CN113261155A

CN113261155A - Electrochemical devices and related articles, components, configurations, and methods

Info

Publication number: CN113261155A
Application number: CN201980086602.4A
Authority: CN
Inventors: 迈克尔·G·拉拉米; 丹尼尔·G·米洛巴; 尤里·V·米哈利克; 查里克莱亚·斯科尔迪利斯-凯莱; 沙恩·哈勒尔
Original assignee: Sion Energy Co ltd
Current assignee: Sion Energy Co ltd; Sion Power Corp
Priority date: 2018-12-27
Filing date: 2019-12-23
Publication date: 2021-08-13
Also published as: EP3903368A2; JP2022516102A; KR20210108453A; WO2020139802A3; WO2020139802A2

Abstract

Articles including electrodes and current collectors, and associated systems and methods, are provided that are arranged such that at least one electrode can be electrically isolated from the article and/or other components of an electrochemical device. In some cases, the article includes a substrate, the change in volume of the substrate causing at least one electrode to become electrically isolated from the article and/or other components of the electrochemical device. In some cases, heating the substrate causes a change in volume of the substrate. Articles and electrochemical devices including the electrodes, current collectors, heaters, and/or sensors, and related systems and methods, are also provided. Electrochemical devices including electrodes and current collectors arranged in a folded configuration, and related articles, systems, and methods, are also provided.

Description

Electrochemical devices and related articles, components, configurations, and methods

RELATED APPLICATIONS

The present application claims priority from U.S. provisional application No. 62/785,332 entitled "isolated electric Devices and Associated Electrodes and Methods" filed on 27.12.2018, U.S. section 119(e), U.S. provisional application No. 62/785,335 entitled "electric Devices, Heaters, Sensors, and Associated Electrodes and Methods" filed on 27.12.2018, and U.S. provisional application No. 62/785,338 entitled "food electric Devices and Associated Methods and Systems" filed on 27.12.2018, which are filed on 27.12.35.S. section 119(e), the entire contents of each of which are incorporated herein by reference for all purposes.

Technical Field

Articles, devices, systems, and methods related to the construction of electrodes, heaters, sensors, current collectors, and/or substrates in electrochemical devices are generally described.

Background

A typical battery or battery pack includes: an electrochemical cell comprising an anode and a cathode that participate in a chemical reaction. Batteries comprising a plurality of electrochemical cells are typically constructed with a stacked structure involving a plurality of discrete anodes, cathodes, and current collectors. Such a stacked configuration may be difficult or uneconomical to manufacture, and the provision of power to an external device through an external circuit having a stacked configuration requires the formation of many individual electrical connections. Furthermore, in batteries comprising a plurality of electrochemical cells with typical arrangements, problems of a single electrode or cell (e.g. short circuits) can lead to the propagation of faults or even thermal runaway (thermal runaway) throughout the entire battery from the initially problematic cell to other cells, which can rapidly degrade the performance of the battery and even cause safety hazards. Additionally, in some situations, it may be desirable to maintain or change the temperature of the battery, as well as detect changes in temperature or pressure during operation of the battery.

Accordingly, improved articles, devices, systems, and methods are desired.

Disclosure of Invention

Articles including electrodes and current collectors, and related devices, systems, and methods, are provided that are arranged such that at least one electrode can be electrically isolated from the article and/or other components of an electrochemical device. In some cases, the article includes a substrate, the change in volume of the substrate causing at least one electrode to become electrically isolated from the article and/or other components of the electrochemical device. In some cases, heating the substrate causes a change in the volume of the substrate.

Articles and electrochemical devices including the electrodes, current collectors, heaters, and/or sensors, and related systems and methods, are also provided. The sensor, when present, may be a temperature sensor or a pressure sensor. In some cases, the heater and/or sensor is adjacent to the article or electrochemical device. In some cases, the heater and/or sensor is a thin film integrated into the article or electrochemical device.

Electrochemical devices including electrodes and current collectors arranged in a folded configuration, and related articles, systems, and methods are also provided. In some cases, the electrochemical device includes one or more continuous components, such as continuous electrodes, current collectors, separators, and/or substrates. In some cases, the electrochemical device is constructed and arranged to apply an anisotropic force (e.g., in a direction perpendicular to the active surface of the anode). In some cases, the electrochemical device includes an oversized anode.

In some cases, the subject matter of the present disclosure relates to interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.

In one aspect, an article is provided. In some embodiments, the article comprises a substrate. In some cases, the article includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, the article comprises a current collector domain. The collector field may include a collector bus electronically coupled to the discrete electrode segments. In some embodiments, the current collector domain comprises a plurality of current collector segments. Each current collector segment may be electronically coupled to an electrode segment. In some embodiments, for each of the collector segments, the collector segment is electronically coupled to the collector bus via at least one collector bridge.

In another aspect, an article is provided. In some embodiments, the article comprises a substrate. In some cases, the article includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, the article comprises a current collector domain. The collector field may include a collector bus electronically coupled to the discrete electrode segments. In some embodiments, the article is configured such that: when the temperature of the article reaches the threshold temperature, at least one of the collector segments is no longer electronically coupled to the collector bus due, at least in part, to the thermally-induced volumetric change of the substrate.

In another aspect, a method is provided. In some embodiments, a method includes changing a volume of a substrate that is part of an electrochemical device during charging and/or discharging of the electrochemical device. In some cases, an electrochemical device includes a substrate. In some cases, the electrochemical device includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, an electrochemical device includes a collector domain including a collector bus electronically coupled to discrete electrode segments. In some embodiments, changing the volume of the substrate causes, at least in part, a loss of electronic coupling between at least one of the electrode segments and the current collector bus.

In another aspect, an article is provided. In some embodiments, the article comprises a substrate. In some cases, the article includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, the article comprises a current collector domain. In some cases, the collector domain includes a collector bus electronically coupled to the discrete electrode segments. In some embodiments, the article includes a heater adjacent to the substrate. In some cases, the heater is configured to heat at least a portion of the article.

In another aspect, an article is provided. In some embodiments, the article comprises a substrate. In some cases, the article includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, the article comprises a current collector domain. In some cases, the collector domain includes a collector bus electronically coupled to the discrete electrode segments. In some embodiments, the article includes one or more sensors adjacent to the substrate. In some cases, the one or more sensors are configured to respond to a condition of the article.

In another aspect, a method is provided. In some embodiments, the method includes heating at least a portion of the electrochemical device using a heater that is part of the electrochemical device. In some cases, an electrochemical device includes a substrate. In some embodiments, the electrochemical device includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, an electrochemical device includes a current collector domain. In some cases, the collector domain includes a collector bus electronically coupled to the discrete electrode segments.

In another aspect, a method is provided. In some embodiments, the method includes detecting a condition of the electrochemical device based at least in part on a signal from a sensor that is part of the electrochemical device. In some cases, an electrochemical device includes a substrate. In some embodiments, the electrochemical device includes a plurality of discrete electrode segments adjacent to the substrate. The electrode segments may include an electrode active material. In some embodiments, an electrochemical device includes a current collector domain. In some cases, the collector domain includes a collector bus electronically coupled to the discrete electrode segments.

In another aspect, an electrochemical device is described. In some embodiments, an electrochemical device includes a first anode portion including a first anode active surface portion. In some cases, the electrochemical device includes a second anode portion including a second anode active surface portion, the second anode active surface portion facing the first anode active surface portion. In some embodiments, the electrochemical device comprises a third anode portion comprising a third anode active surface portion. In some cases, the third anode active surface portion faces away from both the first anode active surface portion and the second anode active surface portion. In some embodiments, the electrochemical device comprises a fourth anode portion comprising a fourth anode active surface portion. In some cases, the fourth anode active surface portion faces both the first anode active surface portion and the third anode active surface portion. In some cases, the third anode portion is positioned at least partially between the first anode portion and the fourth anode portion. In some embodiments, the electrochemical device includes a first cathode portion including a first cathode active surface portion facing a first anode active surface portion. In some embodiments, the electrochemical device includes a second cathode portion including a second cathode active surface portion facing a second anode active surface portion. In some cases, the electrochemical device includes a third cathode portion including a third cathode active surface portion facing the third anode active surface portion. In some cases, the electrochemical device includes a fourth cathode portion including a fourth cathode active surface portion facing the fourth anode active surface portion. In some embodiments, the electrochemical device comprises a separator arranged such that a first portion of the separator is between the first anode portion and the first cathode portion, a second portion of the separator is between the second anode portion and the second cathode portion, a third portion of the separator is between the third anode portion and the third cathode portion, and a fourth portion of the separator is between the fourth anode portion and the fourth cathode portion. In some embodiments, the electrochemical device is constructed and arranged to: applying an anisotropic force having a component perpendicular to the first anode active surface portion for at least one period of time during charging and/or discharging of the device.

In another aspect, an electrochemical device is described. In some embodiments, an electrochemical device includes a plurality of anode portions, a plurality of cathode portions, and a serpentine separator. In some embodiments, the electrochemical device comprises the following parts arranged in the order listed: a first anode portion comprising a first anode active surface portion; a first spacer portion; a first cathode portion comprising a first cathode active surface portion; a second cathode portion comprising a second cathode active surface portion; a second spacer portion; a second anode portion comprising a second anode active surface portion; a third anode portion comprising a third anode active surface portion; a third spacer portion; a third cathode portion comprising a third cathode active surface portion; a fourth cathode portion comprising a fourth cathode active surface portion; a fourth spacer portion; and a fourth anode portion comprising a fourth anode active surface portion. In some embodiments, the electrochemical device is constructed and arranged to apply an anisotropic force having a component perpendicular to the first anode active surface portion for at least one period of time during charging and/or discharging of the device.

In another aspect, an electrochemical device is described. In some embodiments, an electrochemical device includes a first anode portion including a first anode active surface portion. In some cases, the electrochemical device includes a second anode portion including a second anode active surface portion, the second anode active surface portion facing the first anode active surface portion. In some embodiments, the electrochemical device comprises a third anode portion comprising a third anode active surface portion. In some cases, the third anode active surface portion faces away from both the first anode active surface portion and the second anode active surface portion. In some embodiments, the electrochemical device comprises a fourth anode portion comprising a fourth anode active surface portion. In some cases, the fourth anode active surface portion faces both the first anode active surface portion and the third anode active surface portion. In some cases, the third anode portion is positioned at least partially between the first anode portion and the fourth anode portion. In some embodiments, the electrochemical device includes a first cathode portion including a first cathode active surface portion facing a first anode active surface portion. In some embodiments, the electrochemical device includes a second cathode portion including a second cathode active surface portion facing a second anode active surface portion. In some cases, the electrochemical device includes a third cathode portion including a third cathode active surface portion facing the third anode active surface portion. In some cases, the electrochemical device includes a fourth cathode portion including a fourth cathode active surface portion facing the fourth anode active surface portion. In some embodiments, the electrochemical device comprises a separator arranged such that a first portion of the separator is between the first anode portion and the first cathode portion, a second portion of the separator is between the second anode portion and the second cathode portion, a third portion of the separator is between the third anode portion and the third cathode portion, and a fourth portion of the separator is between the fourth anode portion and the fourth cathode portion. In some embodiments, the electrochemical device comprises a cumulative cathode active surface perimeter defined by a sum of perimeters of all cathode active surfaces of the electrochemical device. In some cases, at least 60% of the cumulative cathode active surface perimeter overlaps the anode active surface.

In another aspect, an electrochemical device is described. In some embodiments, an electrochemical device includes a plurality of anode portions, a plurality of cathode portions, and a serpentine separator. In some embodiments, the electrochemical device comprises the following parts arranged in the order listed: a first anode portion comprising a first anode active surface portion; a first spacer portion; a first cathode portion comprising a first cathode active surface portion; a second cathode portion comprising a second cathode active surface portion; a second spacer portion; a second anode portion comprising a second anode active surface portion; a third anode portion comprising a third anode active surface portion; a third spacer portion; a third cathode portion comprising a third cathode active surface portion; a fourth cathode portion comprising a fourth cathode active surface portion; a fourth spacer portion; and a fourth anode portion comprising a fourth anode active surface portion. In some embodiments, the electrochemical device comprises a cumulative cathode active surface perimeter defined by a sum of perimeters of all cathode active surfaces of the electrochemical device. In some cases, at least 60% of the cumulative cathode active surface perimeter overlaps the anode active surface.

Other advantages and novel features of the invention will become apparent from the following detailed description of various non-limiting embodiments of the invention when considered in conjunction with the drawings. In the event that the present specification and the documents incorporated by reference include conflicting and/or inconsistent disclosure, the present specification shall control.

Drawings

Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying drawings, which are schematic and are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated is typically represented by a single numeral. For purposes of clarity, not every component may be labeled in every drawing, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In the drawings:

fig. 1 is an exemplary schematic diagram depicting a top view of an article according to certain embodiments;

fig. 2A is an exemplary schematic diagram depicting a top view of an article according to certain embodiments;

fig. 2B is an exemplary schematic diagram depicting a cross-sectional side view of an article according to certain embodiments;

fig. 2C is an exemplary schematic diagram depicting a side view of an article according to certain embodiments;

FIG. 3 is an exemplary schematic diagram depicting a top view of an article according to certain embodiments;

FIG. 4 is an exemplary schematic diagram illustrating a cross-sectional side view of an electrochemical device according to certain embodiments;

FIG. 5 is an exemplary schematic diagram depicting a cross-sectional side view of an article according to certain embodiments;

fig. 6A is an exemplary schematic depicting a side view of an electrochemical device according to certain embodiments;

fig. 6B is an exemplary schematic diagram depicting a side view of an electrochemical device according to certain embodiments;

fig. 7A is an exemplary schematic diagram depicting a side view of a portion of an article according to certain embodiments;

fig. 7B is an exemplary schematic diagram depicting a side view of a portion of an article according to certain embodiments;

fig. 8A is an exemplary schematic diagram depicting a side view of a portion of an article according to certain embodiments;

FIG. 8B is an exemplary schematic diagram depicting a side view of a portion of an article according to one set of embodiments;

fig. 9A is an exemplary schematic depicting a cross-sectional side view of a portion of a partially expanded electrochemical device, in accordance with certain embodiments;

FIG. 9B is an exemplary schematic diagram depicting a cross-sectional side view of a portion of a folded electrochemical device according to one set of embodiments;

Fig. 10A is an exemplary schematic depicting a cross-sectional side view of a portion of a partially expanded electrochemical device, in accordance with certain embodiments;

fig. 10B is an exemplary schematic depicting a cross-sectional side view of a portion of a folded electrochemical device, according to some embodiments;

11A-11B depict schematic diagrams illustrating cathode active surfaces and cathode active surface perimeters, according to certain embodiments; and

fig. 12 depicts a schematic diagram showing a cathode active surface and an anode active surface overlapping at least some of the perimeter of the cathode active surface, according to some embodiments.

Detailed Description

Articles including electrodes and current collectors, and related devices, systems, and methods, are provided that are arranged such that at least one electrode can be electrically isolated from the article and/or other components of an electrochemical device. In some cases, an article includes a substrate (e.g., a polymeric material), a current collector bus, and a plurality of discrete electrode segments (e.g., including an electrode active material, such as lithium and/or a lithium alloy) adjacent to the substrate and electrically coupled to the current collector bus. At least some of the electrode segments may be electrically decoupled from the collector bus at least in part due to changes in the volume of the substrate. In some cases, altering the volume of the substrate may involve heating the article (e.g., causing thermally-induced expansion or contraction of the substrate) to provide electrically isolated electrodes (e.g., problematic electrodes, such as electrodes that are part of a short circuit) in a simple, economical manner. Configurations of the articles described herein may include the use of discrete current collector segments and current collector bridges electrically coupled to a current collector bus, and/or a continuous component (e.g., a continuous substrate and/or a continuous current collector bus). In certain embodiments, the article may include a heater and/or a sensor (e.g., a temperature sensor or a pressure sensor) adjacent to the substrate. The articles provided herein can be useful when included in an electrochemical device (e.g., a multi-cell battery, such as a rechargeable lithium battery). In certain embodiments, the article may include a heater and/or a sensor (e.g., a temperature sensor or a pressure sensor) adjacent to the substrate.

In some cases, the electrochemical devices (and articles contained therein) may be arranged in a folded configuration and may be manufactured without the need for complex and/or expensive manufacturing procedures. In some such cases, the folded (or foldable) electrochemical device is constructed and arranged to apply (e.g., for at least one period of time during charging and/or discharging) an anisotropic force having a component that is perpendicular to a portion of the electrochemical device (e.g., an anode active surface portion). In some cases, configurations of anodes and cathodes are employed to mitigate problems associated with certain anode active materials (e.g., lithium or lithium alloys). For example, in some cases, folded electrochemical devices are provided that include an "oversized" anode.

For multi-cell batteries comprising multiple anodes and cathodes, a common problem is to remove the problematic electrodes from the entire electrical circuit before the problematic electrodes cause substantial damage to the entire battery. One way in which the electrodes may be problematic is when they reach too high a temperature (e.g., because the electrodes participate in a short circuit). Such problematic electrodes can compromise the performance of the battery and present safety hazards, such as thermal runaway (e.g., in the case of lithium batteries). Therefore, the following electrochemical devices are desired: the electrodes of the electrochemical device may be simply and easily electrically isolated (e.g., upon reaching a certain temperature) without the need for complex and expensive circuitry, arrangements, and/or manufacturing procedures. According to some, but not necessarily all, embodiments, the articles, systems, and methods described herein provide a simple, economical, and efficient way to electrically isolate an electrode from a current collector (e.g., a current collector bus) and/or other components. For example, arranging an article having a current collector bus and a plurality of discrete electrode segments adjacent to a substrate allows for, in some cases, a change in volume of the substrate (e.g., a thermally-induced change in volume of the substrate) to electrically decouple at least one of the discrete electrode segments from the current collector bus, thus isolating the electrode segment from the system.

While typical cells are constructed in a stacked configuration and thus require careful, expensive, and often wasteful manufacturing and placement steps, in some cases, the articles and electrochemical devices described herein may be arranged and constructed with certain continuous components, such as a continuous substrate, electrodes, current collectors, and/or separators. The use of some such continuous components may reduce the cost and manufacturing time for the battery and provide a configuration that may improve functionality. For example, a plurality of discrete electrodes may be electrically coupled to a continuous current collector bus, thus providing a simple design for an article having electrically isolatable electrodes. Additionally, in some cases, cells having continuous components may be arranged to be folded rather than stacked, which may increase manufacturing speed, reduce cost, and increase tolerances. In some cases, an anisotropic force is applied to a folded electrochemical device described herein. In addition, in some, but not necessarily all, embodiments, the electrodes of the folded electrochemical device are arranged and configured such that a relatively large proportion of the cumulative perimeter of the cathode active surface overlaps the anode, which in some cases may reduce certain problems, such as over-utilization or uneven utilization, that occur during operation of the folded electrochemical device.

In some embodiments, articles, devices, systems, and methods relating to the construction of electrodes, substrates, current collectors, and related components are generally described. Fig. 1 includes a schematic illustration of an article 100 according to one set of embodiments. In some cases, the article may be used as a component in an electrochemical device. The article may include a plurality of components, such as a substrate, an electrode, and/or a current collector domain in the inventive construction.

In some embodiments, the article comprises a substrate. Referring again to fig. 1, in some embodiments, article 100 includes a substrate 120. In some embodiments, other components of the article, such as electrodes, current collector domains, and the like, may be disposed on the substrate. The substrate may be made of any of a number of suitable materials, for example, materials that can undergo a change in volume, as will be described in more detail below. In some embodiments, the substrate is a film (e.g., a polymer film or a ceramic film). The substrate may be a single sheet of material or the substrate may be a multi-layered composite. In certain embodiments, the substrate comprises at least one domain or layer that is electronically non-conductive. In some, but not necessarily all, embodiments, the substrate is flexible (e.g., has sufficient flexibility to fold without substantial failure). In some, but not necessarily all, embodiments, the substrate is or includes a release layer. For example, according to certain embodiments, the substrate 120 in fig. 1 is a release layer.

In some embodiments, the article includes a plurality of discrete electrode segments adjacent to the substrate. As shown in fig. 1, the article 100 includes a plurality of discrete electrode segments 130 adjacent to the substrate 120. The electrode segments may be formed directly on the substrate (e.g., by a deposition or coating process), or one or more intervening layers may be present between the substrate and adjacent electrode segments. The plurality of discrete electrode segments adjacent to the substrate may be within a relatively small distance of the substrate (e.g., in embodiments involving compact, energy-intensive designs). For example, each of the plurality of discrete electrode segments may be within 5.0mm, within 3.0mm, within 2.0mm, within 1.0mm, within 0.5mm, within 0.3mm, within 0.2mm, within 0.1mm, or less of the substrate. In some embodiments, each of the plurality of discrete electrode segments is an anode, and in some embodiments, each of the plurality of discrete electrode segments is a cathode. In certain embodiments, the plurality of discrete electrodes includes both a cathode and an anode.

In some embodiments, the electrode segments comprise an electrode active material. As used herein, the term "electrode active material" refers to any electrochemically active material associated with an electrode. For example, "cathode active material" refers to any electrochemically active material associated with the cathode, while "anode active material" refers to any electrochemically active material associated with the anode. In some embodiments, the electrode segments comprise lithium metal and/or lithium alloy as the electrode active material (e.g., as the anode active material). Suitable cathode active materials and anode active materials are described more fully below.

As used herein, the term "discrete" with respect to the plurality of discrete electrode segments described above is used to mean that each electrode segment of the plurality of discrete electrode segments is distinct and spatially separated from other electrode segments of the plurality of discrete electrode segments. For example, referring to fig. 1, the plurality of discrete electrode segments 130 includes an electrode segment 130a and an electrode segment 130b, and the electrode segment 130a is distinct and spatially separated from the electrode segment 130 b. In some embodiments, the discrete electrode segments are arranged such that the segments are not connected to each other via regions comprising electrode active material. In some cases, when the article described herein is used as part of an electrochemical device (e.g., a device comprising one or more electrochemical cells, such as a battery, when loaded with an electrolyte), no two discrete electrode segments are in direct physical contact with each other, even, for example, if and when the article is folded. Further, any electronic coupling between any two discrete electrode segments involves the transport of electrons through at least one other component than the coupled electrode segments, such as the current collector domain of the article. According to certain embodiments, having an article include a plurality of discrete electrode segments rather than a plurality of non-discrete electrode segments allows for the individual electrode segments to be electrically isolated from other components of the article, such as other electrode segments and/or a current collector bus (described more fully below), in certain instances.

In some embodiments, the article comprises a current collector domain. For example, referring to fig. 1, according to certain embodiments, article 100 includes a current collector region 125 adjacent to substrate 120. The current collector domain may collect current generated by a plurality of discrete electrode segments and may provide an effective surface for attaching electrical contacts to an external circuit (e.g., when the article is used as part of an electrochemical device, such as a battery). Thus, the current collector domain typically comprises an electronically conductive material. For example, the current collector region may include one or more conductive metals, such as aluminum, copper, chromium, stainless steel, and nickel. In some embodiments, the current collector region comprises a copper metal layer. In some cases, the current collector region includes a plurality of subdomains or substructures, the arrangement and/or configuration of which may be used to allow electrical isolation of individual ones of the plurality of discrete electrode segments (e.g., due to changes in volume of the substrate). For example, the collector domain may include collector segments and/or collector bridges, as described more fully below.

In some embodiments, the collector domain comprises a collector bus. Fig. 1 depicts a collector domain 125, including a collector bus 121, according to some embodiments. In some cases, the collector domain consists entirely of the collector bus (as is the case in fig. 1, according to some embodiments), while in some cases the collector domain includes other structures in addition to the collector bus. The collector bus may be a structure of collector domains that form electrical contact with an external circuit (e.g., in the case of an electrochemical device such as a battery). In some cases, the collector bus is continuous, as described in more detail below.

In some embodiments, the collector bus is electronically coupled to the discrete electrode segments (e.g., from a plurality of discrete electrode segments). For example, referring to fig. 1, according to certain embodiments, article 100 comprises: a plurality of discrete electrode segments 130; and a collector domain 125 including a collector bus 121, and the collector bus 121 is electrically coupled to the plurality of discrete electrode segments 130. The electronic coupling between the discrete electrode segments and the collector bus may allow the generated current at the electrode segments to flow to the collector bus, which may be in electrical contact with an external circuit. In some cases, the electronic coupling may be established by direct physical contact between the discrete electrode segments and the current collector bus. For example, referring to fig. 1, a discrete electrode segment of the plurality of discrete electrode segments 130 is in direct physical contact with the collector bus 121 and is thus electrically coupled to the collector bus 121. However, in some cases, the electronic coupling between the discrete electrode segments and the collector bus occurs via one or more additional intermediate structures of the collector domain, as will be described more fully below.

In some cases, a loss of electronic coupling between the collector bus and at least one of the plurality of discrete electrode segments may occur. This loss of electronic coupling may result in at least one of the discrete electrode segments being electrically isolated from: a collector bus, other discrete electrode segments that have not lost electronic coupling with the collector bus, and/or components of an external circuit (e.g., other components of an electrochemical device such as a battery). As described above, isolation of certain electrode segments may be useful for removing problematic electrodes from the overall circuit while allowing, for example, the electrochemical device to continue charging and/or discharging with sufficient performance.

Some embodiments include changing a volume of a substrate that is part of an electrochemical device during charging and/or discharging of the electrochemical device. The electrochemical device can include an article described herein, the article comprising a substrate described herein. In some cases, changing the volume of the substrate causes, at least in part, a loss of electronic coupling between at least one of the electrode segments and the current collector bus. For example, referring again to fig. 1, in some cases, according to certain embodiments, altering the volume of the substrate 120 of the article 100 during charging and/or discharging of an electrochemical device comprising the article 100 causes, at least in part, a loss of electronic coupling between the discrete electrode segments 130a and the current collector bus 121. In this way, changes in the volume of the substrate may be used to electrically isolate certain discrete electrode segments during charge and/or discharge cycles (e.g., for safety reasons).

In certain embodiments, altering the volume of the substrate comprises increasing the volume of the substrate. As an example and according to certain embodiments, in fig. 1, the current collector bus 121 is a layer of conductive metal (e.g., copper) coated on the substrate 120, and the plurality of discrete electrode segments 130 comprise discrete layers comprising an electrode active material (e.g., lithium and/or lithium alloy) in direct physical contact with the current collector bus 121. As the volume of the substrate 120 increases (e.g., expands), at least one of the discrete electrode segments (e.g., discrete electrode segment 130a) in the plurality of discrete electrode segments 130 may lose electronic coupling with the current collector bus 121 due, at least in part, to the increase in volume of the substrate (e.g., due to the formation of gaps and thus loss of direct physical contact between the at least one of the discrete electrode segments and the current collector bus 121).

In certain embodiments, altering the volume of the substrate comprises reducing the volume of the substrate. As an example and according to certain embodiments, in fig. 1, the current collector bus 121 is a layer of conductive metal (e.g., copper) coated on the substrate 120, and the plurality of discrete electrode segments 130 comprise discrete layers comprising an electrode active material (e.g., lithium and/or lithium alloy) in direct physical contact with the current collector bus 121. As the volume of the substrate 120 decreases (e.g., shrinks/shrinks), at least one of the discrete electrode segments (e.g., discrete electrode segment 130a) in the plurality of discrete electrode segments 130 may lose electronic coupling with the current collector bus 121 due, at least in part, to the decrease in volume of the substrate (e.g., due to delamination of the at least one of the discrete electrode segments and thus loss of direct physical contact between the at least one of the discrete electrode segments and the current collector bus 121).

In some cases, altering the volume of the substrate includes heating the substrate. In other words, the change in volume of the substrate may occur at least in part due to thermal expansion or contraction of the substrate. For example, referring to fig. 1, heating the substrate 120 (or a portion thereof) may cause a change in the volume of the substrate 120. In some cases, heating the substrate may include applying heat from a heater, which may be a component external to the article, or a component integrated into the article, as described more fully below. However, in certain embodiments, heating the substrate includes charging and/or discharging the electrochemical device such that heat is generated by the charging and/or discharging. For example, in some cases, a short circuit may occur between at least one of the discrete electrode segments and another component of the electrochemical device, resulting in resistive heating that heats the substrate and thus changes the volume of the substrate.

It should be understood that in some instances, heating a component of an electrochemical device or article described herein may result in a loss of electronic coupling between the discrete electrode segments and the current collector bus due to melting or thermal shock of the component (either a portion of the discrete electrode segments or a portion of the current collector bus). While this phenomenon may occur in some cases during heating of the substrate, embodiments described herein involve a loss of electronic coupling that occurs at least in part due to a change in volume of the substrate. Non-limiting reasons for the loss of electronic coupling due to the change in volume of the substrate will be described in more detail below.

In certain embodiments, the articles described herein are configured such that when the temperature of the article reaches a threshold temperature, at least one of the electrode segments is no longer electrically coupled to the current collector bus due, at least in part, to the thermally-induced volume change of the substrate. For example, referring to fig. 1, according to some embodiments, the article 100 is configured such that when the article 100 reaches a threshold temperature, at least one of the electrode segments (e.g., discrete electrode segment 130a) of the plurality of discrete electrode segments 130 is no longer electrically coupled to the current collector bus 121 due, at least in part, to thermally-induced volumetric changes of the substrate. By way of non-limiting example, in some cases, the threshold temperature is 65 ℃. In this case, if the temperature of the article increases (e.g., due to a short circuit of an external heat source and/or electrochemical device), once the temperature reaches 65 ℃, the at least one electrode segment will become electrically decoupled from the current collector bus at least in part due to the thermally-induced volumetric change of the substrate.

The article may be configured to: losses in electronic coupling between at least one of the discrete electrode segments and the current collector bus are experienced due, at least in part, to thermally-induced volumetric changes of the substrate, for example, by selecting a particular component, such as the substrate, to include one or more materials having a coefficient of thermal expansion of a relatively large magnitude. Additionally or alternatively, the article may be configured to cause a mismatch between the coefficients of thermal expansion of two or more components of the article (e.g., one or more structures of the substrate and current collector domains) such that the two or more components expand at different rates during the heating process, resulting in mechanical failure of the components and thus loss of electrical coupling. Exemplary configurations of articles are described in more detail below, which in some embodiments may be subject to loss of electronic coupling between at least one of the electrode segments and the current collector domain when the temperature of the article reaches a threshold temperature.

It should be understood that in some embodiments, the threshold temperature at which loss of electronic coupling occurs between the discrete electrode segments and the current collector domain depends on the materials used for the components of the article (e.g., substrate, electrode segments, current collector domain, etc.) and the geometry and dimensions of the components. The threshold temperature is the absolute temperature at which the loss of electronic coupling described herein and elsewhere occurs. It should be understood that the threshold temperature considered herein refers to the temperature of one or more components of the article, and not the ambient temperature (e.g., the temperature of the environment or surroundings in which the article and/or the electrochemical device including the article is located). In some embodiments, the threshold temperature is a temperature of a substrate of the article. In some embodiments, the threshold temperature is the temperature of the current collector domain. In some embodiments, the threshold temperature is a temperature of at least one of the plurality of discrete electrode segments.

In some embodiments, the article is configured such that, when subjected to a threshold temperature change, at least one of the electrode segments is no longer electrically coupled to the current collector bus due, at least in part, to thermally-induced volumetric changes of the substrate. The threshold temperature change is relative to an initial temperature at which there is no internal mechanical stress (e.g., compression, tension, shear, bending, torsion, etc.) in the article.

As described above, in some cases, the current collector domain includes a plurality of substructures that can help to electrically isolate one or more discrete electrode segments under certain conditions (e.g., upon thermally-induced volumetric changes of the substrate).

In some embodiments, the current collector domain comprises a plurality of current collector segments. For example, fig. 2A depicts an article 100 comprising a current collector domain 125, wherein the current collector domain 125 comprises, in addition to a current collector bus 121: a plurality of collector segments comprising collector segment 122. As in the case of other configurations of the collector domain, the collector segments include and/or are made of an electronically conductive material, such as an electronically conductive metal (e.g., copper). The current collector segments can be made, for example, by patterned deposition of an electron conducting material (e.g., as a film) on a substrate (e.g., a release layer), as described below. In some embodiments, the current collector segments are separated by voids or gaps. For example, in fig. 2A, the current collector segment 122 is separated from the nearest adjacent current collector segment by a void in the conductive material (which in some cases exposes a portion of the substrate 120). The presence of voids or gaps between the current collector segments allows the current collector segments to be electronically isolated from one another under certain conditions (e.g., upon thermally induced volumetric changes of the substrate).

In some embodiments, each current collector segment is electrically coupled to an electrode segment. Referring again to fig. 2A, article 100 includes: a plurality of discrete electrode segments 130 comprising discrete electrode segments 130 a; and a plurality of collector segments including collector segment 122, and the collector segment 122 is electrically coupled to the discrete electrode segment 130 a. The electronic coupling between the collector segments and the electrode segments may allow the generated current at the electrode segments to flow to the collector segments, which may be electronically coupled with other components of the collector domain, such as a collector bus.

In some embodiments, for each current collector segment, the current collector segment is at least partially disposed between the substrate and the electrode segment to which the current collector segment is electronically coupled. Fig. 2B depicts a side view of the example article 100, where the current collector segment 122 is at least partially disposed between the electrode segment 130a and the substrate 120. Such a configuration may allow for a relatively large contact area between the electrode segments and the current collector segments while still making the active surface of the electrode segments facing away from the current collector segments relatively large, which may be useful in applications such as electrochemical devices. As used herein, the term "active surface" is used to describe the surface of an electrode that may be in physical contact with an electrolyte when the article is part of an electrochemical cell and where electrochemical reactions may occur. Having a relatively large contact area between the electrode segments and the collector segments may allow for an efficient transfer of the generated current generated at the electrode segments to the collector domain.

In some embodiments, for each of the collector segments, the collector segment is electronically coupled to the collector bus via at least one collector bridge. In other words, in some embodiments, any flow path of current from the collector segments to the collector bus must pass through at least one collector bridge. A collector bridge is a substructure of a collector domain that is at least partially disposed between a collector segment and a collector bus. Fig. 2A depicts a plurality of collector bridges, including collector bridge 123. A collector bridge 123 is disposed between the collector segments 122 and the collector bus 121. Fig. 2B shows a side view of a cross-section of an exemplary article 100, where a current collector bridge 123 is disposed between the current collector segment 122 and the current collector bus 121. According to certain embodiments, the collector segments 122 are electronically coupled to the collector bus 121 via a collector bridge 123. The current collector bridge may include an electronically conductive material (e.g., an electronically conductive metal such as copper). As in the case of the current collector segment, the current collector bridge may be fabricated by, for example, patterned deposition of an electron conducting material (e.g., as a film) on a substrate (e.g., a release layer). In some cases, the current collector bridge has a relatively small thickness, as will be described in more detail below. In some cases, each collector bridge is in direct physical contact with the associated collector segment and the collector bridge. However, in certain embodiments, other intermediate materials (e.g., electronically conductive materials) or structures may be at least partially disposed between the current collector bridge and the associated current collector segment and/or current collector bus.

In some embodiments, for each discrete electrode segment of the plurality of discrete electrode segments, the discrete electrode segment is electronically coupled to the collector bus via at least one collector segment. In other words, in certain embodiments, any flow path of current generated at a discrete electrode segment of the plurality of discrete electrode segments to the collector bus must pass through at least one collector segment. For example, referring again to fig. 2A and 2B, according to certain embodiments, any flow path of current generated at the discrete electrode segment 130a (e.g., during discharge of the electrochemical cell) to the collector bus 121 must pass through the collector segment 122. In some cases, the article is configured such that any flow path of current generated at the discrete electrode segments to the collector bus must also pass through both the at least one collector segment associated with the discrete electrode and the collector bridge electrically coupling the collector segment to the collector bus. For example, referring to fig. 2A and 2B, according to some embodiments, any flow of current generated at the discrete electrode segment 130a to the collector bus 121 must include: transferring charge from the discrete electrode segment 130a to the collector segment 122; transferring charge from the collector segments 122 to the collector bridge 123; finally, the charge is transferred from the collector bridge 123 to the collector bus 121. Some such configurations of the articles described herein involve discrete electrode segments, current collector segments, and current collector bridges, each of which is electronically coupled to a current collector bus, but separated, for example, by a void or gap, may allow for convenient electrical isolation of individual discrete electrode segments (e.g., produced by changing the volume of the substrate and thus destroying the current collector bridge associated with the discrete electrode segment).

In some embodiments, changing the volume of the substrate at least partially causes at least one of the collector bridges to no longer couple the collector segment associated with that collector bridge to the collector bus. This loss of electronic coupling between the collector segments and the collector bus can result in a loss of coupling between the discrete electrode segments associated with the collector segments and the collector bus, thereby electrically isolating the electrode segments. For example, referring to fig. 2A, changing the volume of the substrate 120 at least partially causes the collector bridge 123 to no longer couple the collector segment 122 to the collector bus 121, thereby electrically isolating the discrete electrode segments 130 a. The change in volume of the substrate may cause the collector bridge to no longer couple the collector segments to the collector bus by causing, for example, mechanical failure of the collector bridge (e.g., fracture caused by ultimate tensile or compressive failure of the collector bridge) or physical isolation of the collector bridge from one or both of the collector segments and the collector bus (e.g., via delamination).

As described above, in some cases, altering the volume of the substrate involves heating the substrate (e.g., heating the substrate such that it reaches a threshold temperature during charging and/or discharging of an electrochemical device including the article having the substrate). In some embodiments, the heat-induced change in volume of the substrate is an increase in volume of the substrate. For example, in some embodiments, the substrate has a positive coefficient of thermal expansion (e.g., at a threshold temperature), and heating the substrate causes thermal expansion of the substrate. For example, in some embodiments, the substrate 120 comprises a material having a positive coefficient of thermal expansion, and heating the substrate 120 causes an increase in the volume of the substrate 120. However, in some embodiments, the heat-induced change in volume of the substrate is a decrease in volume of the substrate. For example, in some cases, the substrate has a negative coefficient of thermal expansion at a threshold temperature. For example, according to certain embodiments, the substrate 120 comprises a material having a negative coefficient of thermal expansion (e.g., at a threshold temperature), and heating the substrate 120 causes a reduction in the volume of the substrate 120. In some cases, the substrate comprises a heat shrinkable film. In some cases, the substrate comprises a polymeric material, such as polyvinyl alcohol.

In some embodiments, the article is configured such that when the temperature of the article reaches a threshold temperature, at least one of the current collector bridges no longer couples the current collector segment associated with that current collector bridge to the current collector bus due, at least in part, to the thermally-induced volume change of the substrate. Referring to fig. 2A, when the article 100 reaches a certain threshold temperature, the collector bridge 123 no longer electronically couples the collector segment 122 to the collector bus 121. Such a configuration may be useful in electronically isolating the discrete electrode segments. For example, in some embodiments, the article is configured such that when the temperature of the article reaches a threshold temperature, at least one of the discrete electrode segments is no longer electronically coupled to the current collector bus due, at least in part, to the thermally-induced volumetric change of the substrate. Referring to fig. 2B, in certain embodiments, the electrode segment 130a is electronically coupled to the collector bus 121 via the collector segment 122 and the collector bridge 123. In some cases, when the article 100 reaches (e.g., heats up to) the threshold temperature and the collector bridge 123 no longer electronically couples the collector segments 122 to the collector bus 121, there is no electronically conductive path for the current generated at the discrete electrodes 130a to reach the collector bus 121, thereby electronically isolating the discrete electrode segments 130 a.

In some embodiments, the article is configured such that the threshold temperature referred to herein falls within a temperature range. For example, the article can be configured such that the threshold temperature is sufficiently high such that loss of electronic coupling between the discrete electrode segments and the current collector bus (e.g., due to a change in volume of the substrate) does not occur during normal operation of an electrochemical device including the article (e.g., normal charging and/or discharging without short circuiting or thermal runaway). Thus, in certain embodiments, the article can be configured such that the threshold temperature of the article is greater than or equal to 50 ℃, greater than or equal to 55 ℃, greater than or equal to 60 ℃, greater than or equal to 70 ℃, greater than or equal to 75 ℃, greater than or equal to 80 ℃, greater than or equal to 85 ℃, greater than or equal to 90 ℃, greater than or equal to 95 ℃, greater than or equal to 100 ℃, or higher. It should be understood that a threshold temperature of an article falling within a temperature range means that a particular temperature of the article configured to undergo at least one electronic decoupling as described herein (e.g., between at least one discrete electrode segment and the current collector bus, between at least one discrete current collector segment and the current collector bus) upon a thermally-induced volumetric change of the substrate falls within the range. An article configured to have a threshold temperature of 65 ℃ (e.g., an article that, when heated, will undergo at least one electrical decoupling as described herein due, at least in part, to changes in the volume of the substrate once the temperature of the article reaches 65 ℃) is one example of an article having a threshold temperature greater than or equal to 50 ℃ because 65 ℃ falls within a range of values greater than or equal to 50 ℃.

In some embodiments, the article may be configured such that the threshold temperature is sufficiently low such that loss of electronic coupling between the discrete electrode segments and the current collector bus occurs at a temperature sufficiently low such that significant damage to the article and/or an electrochemical device comprising the article does not occur prior to loss of coupling. Thus, in certain embodiments, the article can be configured such that the threshold temperature of the article is less than or equal to 150 ℃, less than or equal to 145 ℃, less than or equal to 140 ℃, less than or equal to 130 ℃, less than or equal to 120 ℃, or less. As another non-limiting example, an article configured to have a threshold temperature of 110 ℃ (e.g., an article that, when heated, will undergo at least one electronic decoupling as described herein due, at least in part, to a change in volume of the substrate once the article's temperature reaches 110 ℃), is an article having a threshold temperature less than or equal to 120 ℃ because 110 ℃ falls within a range of values less than or equal to 120 ℃.

The threshold temperature of the articles described herein may be measured, for example, by running a test current between the discrete electrode segments and the current collector bus while raising the temperature of the article (or components thereof). The threshold temperature may be determined by recording the temperature at which a loss of electronic coupling (e.g., interruption of the test current) between at least one of the discrete electrode segments and the current collector bus is observed.

One way in which the article may be configured such that at least one of the current collector bridges no longer couples the current collector segment associated with that current collector bridge to the current collector bus when the temperature of the article reaches a threshold temperature is by selecting the material of the current collector bridge and the material of the substrate to have different coefficients of thermal expansion. The coefficient of thermal expansion may be expressed as a linear coefficient of thermal expansion (related to the fractional change in the length of the material in response to a change in temperature), an area coefficient of thermal expansion (related to the fractional change in the area of the material in response to a change in temperature), and/or a volumetric coefficient of thermal expansion (related to the fractional change in the volume of the material in response to a change in temperature). Unless otherwise indicated, the coefficient of thermal expansion referred to herein corresponds to the coefficient of linear thermal expansion. As such, during the heating process, the volume of the substrate may expand (or contract) to a different extent than the current collector bridge due to the different coefficients of thermal expansion, resulting in a source of mechanical stress that may cause mechanical failure (e.g., cracking or delamination), which may cause a loss of electronic coupling between the current collector segments and the current collector bridge.

In some embodiments, the article is configured such that at least one of the current collector bridges experiences an ultimate tensile failure when the temperature of the article reaches a threshold temperature. Ultimate tensile failure of a material refers to a material breaking (e.g., breaking) as the material undergoes stretching. One non-limiting example of such a configuration is one in which the coefficient of thermal expansion of the substrate is greater than the coefficient of thermal expansion of the at least one current collector bridge. For example, referring to fig. 2A, according to certain embodiments, the substrate 120 may be made of a material having a coefficient of thermal expansion greater than that of the material from which the current collector bridge 123 is made, and the current collector bridge 123 may be attached to the substrate 120 (e.g., directly or via an intermediate bonding layer or domain). When the substrate 120 and the current collector bridge 123 are heated (e.g., via a thermal load), the substrate 120 will expand to a greater extent than the current collector bridge 123, causing the current collector bridge 123 to undergo a stretching that depends on the extent of expansion of the substrate 120. In some cases, the substrate 120 may expand to the extent that: such that the tension applied to the collector bridge 123 is sufficient to cause ultimate tensile failure of the collector bridge 123. Without wishing to be bound by any particular theory, other design factors that may be used to control the likelihood that the collector bridge experiences mechanical failure (e.g., ultimate tensile failure with some change in volume of the substrate) include, but are not limited to, the thickness of the collector bridge, the modulus of elasticity of the collector bridge, and/or the area of the collector bridge.

In some embodiments, at least one of the collector bridges is subject to an extreme tensile failure such that the collector bridge no longer electrically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to thermally-induced volumetric changes of the substrate. Fig. 3 depicts a top view of one example of article 100 after an ultimate tensile failure of current collector bridge 123 due at least in part to a thermally-induced volumetric change of the substrate as described above, in accordance with certain embodiments. As can be seen in fig. 3, an extreme tensile failure of the collector bridge 123 results in a break that causes a complete discontinuity in the collector bridge 123, thereby disrupting the electronic coupling between the collector segment 122 and the collector bus 121, and thus between the discrete electrode segment 130a and the collector bus 121.

In some embodiments, the article is configured such that at least one of the current collector bridges is subject to an extreme compression fault (e.g., an extreme linear compression fault) once the temperature of the article reaches a threshold temperature. Ultimate compression failure of a material refers to a material breaking (e.g., fracturing or buckling) as the material undergoes compression. One non-limiting example of such a configuration is one in which the substrate has a coefficient of thermal expansion that is less than the coefficient of thermal expansion of the at least one current collector bridge. Another non-limiting example of such a configuration is one in which the coefficient of thermal expansion of the substrate is negative (e.g., the substrate is a heat shrink film). In some embodiments, at least one of the collector bridges is subject to an extreme compression failure such that the at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced volume change of the substrate.

In some embodiments, a first component of an article (e.g., a current collector bridge) and a second component of the article (e.g., a substrate) are configured such that the first component and the second component have a difference in thermal expansion, wherein the second component is in direct contact with and attached to the first component. The thermal expansion difference as used herein is expressed as:

wherein A is₁Is the area of the first part, A₂Is the area of the second part, a₁Is the linear expansion coefficient of the first component, a₂Is the linear expansion coefficient of the second part, E₁Is the modulus of elasticity of the first component, E₂Is the modulus of elasticity of the second component, and σ_ult，1Is the ultimate tensile strength of the first component. The difference in thermal expansion depends on the material selected for the first and/or second component and the respective areas of the first and second component. In some, but not necessarily all, embodiments, a change in temperature Δ Τ of a first component and/or a second component of an article causes ultimate tensile failure of the first component if the change in temperature is greater than or equal to the difference in thermal expansion. In other words, in some embodiments, the first component of the article fails in tension (causing, in some cases, a loss of electronic coupling between certain components of the article) if the inequality represented in equation 1 satisfies the following:

In an embodiment satisfying formula 1. If a is₂Greater than a₁The temperature change deltat will cause ultimate tensile failure of the first component (e.g., the collector bridge). In some embodiments, if the geometry and materials selected for the first and second components are known, equation 1 may be used to determine the temperature change required to cause an ultimate tensile failure of the first component.

In some embodiments, the first component (e.g., at least one current collector bridge) and/or the second component (e.g., substrate) has a differential thermal expansion of greater than or equal to 10 ℃, greater than or equal to 15 ℃, greater than or equal to 20 ℃, greater than or equal to 25 ℃, greater than or equal to 30 ℃, greater than or equal to 40 ℃, or more. In some embodiments, the first component (e.g., at least one current collector bridge) and/or the second component (e.g., substrate) has a thermal expansion difference of less than or equal to 100 ℃, less than or equal to 90 ℃, less than or equal to 80 ℃, less than or equal to 70 ℃, less than or equal to 60 ℃, or less. Combinations of the above ranges are possible. For example, in some embodiments, the first component (e.g., at least one current collector bridge) and/or the second component (e.g., substrate) have a difference in thermal expansion greater than or equal to 10 ℃ and less than or equal to 100 ℃.

In some embodiments, the article is configured such that, when the temperature of the article reaches a threshold temperature, at least one of the collector bridges is subject to a change other than an extreme tensile failure or an extreme compressive failure, such that the at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced change in volume of the substrate. For example, in some cases, a change in volume of the substrate causes delamination of the collector bridge such that the collector bridge loses contact with at least one of the collector segments or the collector bus associated with the collector bridge.

In some embodiments, heating of the articles described herein (resulting in a thermally-induced volume change of the substrate) occurs passively. Heating of the article occurs passively if heating of the article occurs without application of a thermal load from the heater described herein. For example, the article may be passively heated due to a failure in an electrochemical device including the article during charging and/or discharging of the electrochemical device, such as when a short circuit and/or thermal runaway occurs (e.g., due to corrosion or fatigue of one or more parts of the electrochemical device). Such processes may cause heating of one or more components of the article, in some cases raising the temperature above a threshold temperature, due to resistive heating and/or heat released from the exothermic chemical reaction.

In some embodiments, at least a portion of the thermally-induced volumetric change of the substrate occurs as a result of an active heating process. The active heating process involves applying a thermal load from a heater. As used herein, a heater is a component that can receive a signal (e.g., an electrical signal) that actuates the heater and causes the heater to apply a thermal load. In some cases, heating of the substrate is accomplished at least in part via the use of a heater that is part of the electrochemical device. In some embodiments, the heater is an external component adjacent to the article. However, in certain embodiments, the heater is a component integrated into the article (e.g., a resistive heater applied as a thin film to one or more layers of the article). In some cases, the substrate itself may be used as a heater if the substrate comprises a material with sufficient electronic conductivity.

In some embodiments, the article includes a heater adjacent to the substrate. In some cases, the article includes a plurality of heaters adjacent to the substrate. As described above, the heater may be configured to heat at least a portion of the articles described herein. For example, fig. 7A illustrates an exemplary article 100 that includes a heater 140 adjacent to the substrate 120, and in some cases, the heater 140 is capable of heating the article 100. In accordance with some, but not necessarily all, embodiments, it may be useful to include heaters in the articles described herein for various reasons. For example, the substrate may be heated using a heater such that a thermally induced volumetric change of the substrate occurs, resulting in a loss of electronic coupling between one or more discrete electrode segments and the current collector bus, as described above in connection with active heating of the article. In some cases, including a heater adjacent to an article (e.g., a substrate) may provide a way to maintain the temperature of the article within a desired range, such as where the article is part of an electrochemical device that may be expected to operate in low ambient conditions (e.g., a battery for an electric vehicle operating in winter). It should be understood that while in some cases the heater is in close proximity to the substrate (e.g., directly attached, coated, or vacuum deposited on the substrate without intervening layers or structures between the heater and the substrate, as shown in fig. 7A and 7B), in some cases the heater is disposed directly on one or more components (e.g., layers) of the article that are not the substrate. Fig. 7A illustrates a plurality of heaters 140, each heater proximate to (but not in direct contact with) a discrete electrode segment and/or a discrete current collector segment, according to some embodiments. In some embodiments, the distance between the heater and the substrate is less than or equal to 5mm, less than or equal to 3mm, less than or equal to 2mm, less than or equal to 1mm, less than or equal to 0.5mm, less than or equal to 0.2mm, less than or equal to 0.1mm, or less.

In some cases, the heater replaces (i.e., "replaces") a component of one or more discrete electrode segments and/or current collector domains in the article structure. For example, in the case where discrete current collector segments are deposited at periodic locations along the substrate during manufacture (e.g., via a jump coating process), one or more of the locations may be masked so that current collector segments are not deposited there, and in a subsequent step, a heater is placed at the one or more locations (e.g., after the masking step).

In some embodiments, the heater is located near one or more of the ends of the article. For example, in some cases, the heater is located within the last 20%, within the last 10%, or within the last 5% of the length of the article. In some, but not necessarily all cases, there are no discrete electrode or current collector segments between the heater and the end of the substrate (referring to the end according to the long axis of the substrate). For example, fig. 7B illustrates a non-limiting embodiment in which the heater 140 is positioned near an end of the article 100 opposite the interior position shown in the illustration, such as fig. 7A. According to some, but not necessarily all, embodiments, placing the heater at or near one end of the article may help to simplify manufacturing (e.g., by potentially avoiding complex masking steps) and allow easy access to the heater even when the article is folded. However, in some cases, placing the heater in an interior location, as shown in fig. 7A, may help provide more uniform heat throughout the article, such as in cases where the article is folded, and allow for localized heating (e.g., proximate to the area of the substrate proximate to a particular current collector bridge, as is the case in some but not necessarily all embodiments). As noted above, and described in more detail below, in some cases, the article is foldable. In some such cases, the heater is positioned between the folded portions of the article as the article is folded. In certain embodiments, such a configuration may allow the heater to easily heat an interior portion (e.g., a folded portion) of the article and/or a folded electrochemical device comprising the article.

In some embodiments, the heater comprises a thin film. In some, but not necessarily all cases, the heater is a thin film. For example, referring to fig. 7A, according to some embodiments, the heater 140 is a thin film. In embodiments where the heater is or includes a thin film, the thin film may be deposited (e.g., by physical or chemical vacuum deposition techniques, spin coating, or other suitable thin film deposition techniques described herein) on a portion of the article. For example, in some cases, the heater is a thin film deposited directly on the substrate (e.g., during fabrication of the substrate). However, in some cases, the thin film of the heater is deposited on one or more other components of the article. In some cases, a plurality of heaters including a film are positioned on the article as a plurality of discrete film segments (e.g., film segments deposited via skip coating or masked coating). According to some, but not necessarily all, embodiments, the use of a heater comprising a film may be beneficial in situations where a relatively high volumetric energy density of the cell comprising the article is desired. In addition, according to certain embodiments, a thin film heater may be useful when integrating the heater into a foldable article, because the thin film may be thin enough to avoid obstructing folding of the article. In some cases, the thickness (e.g., average thickness) of the heater (e.g., thin film heater) is less than or equal to 1mm, less than or equal to 500 μm, less than or equal to 200 μm, less than or equal to 100 μm, less than or equal to 50 μm, less than or equal to 20 μm, less than or equal to 10 μm, less than or equal to 5 μm, less than or equal to 2 μm, less than or equal to 1 μm, less than or equal to 0.5 μm, less than or equal to 200nm, or less. In some cases, the heater has a thickness greater than or equal to 20nm, greater than or equal to 50nm, greater than or equal to 100nm, or greater.

In some cases, the heater comprises a material capable of resistive heating. For example, the heater may be electronically coupled to an external circuit (e.g., via a power cord) such that when current is passed through the circuit, the resistance of the heater causes resistive heating (i.e., joule heating) to occur. In some cases, the heat generated by such resistive heating may heat the article and/or an electrochemical device comprising the article. In some cases, the heater comprises a metal or metal alloy. For example, according to certain embodiments, the heater may include a resistive metal or metal alloy (e.g., a metal or metal alloy having a relatively high resistivity) to facilitate resistive heating. Examples of materials that the heater may comprise include, but are not limited to, nickel alloys (e.g., nichrome, constantan, alvim, etc.), stainless steel, graphite, silicon-based compounds, combinations thereof, and the like. In general, the material for the heater (e.g., a heater comprising a thin film) may be selected based on one or more characteristics including the resistivity of the material, as described in more detail below.

In some embodiments, the heater comprises a wire. For example, in fig. 7A or 7B, according to some but not all embodiments, the heater 140 is a wire, rather than a film. The conductive lines may be deposited on the article (e.g., proximate to the substrate, or on an intermediate layer) to form conductive traces on the article. As in the case of heaters comprising thin films, in some cases, a heater comprising conductive traces may be formed using a patterned mask on the substrate or a layer on the substrate. In some cases, the leads of the heater are electrically coupled to an external circuit, as described above for heaters including thin films, such that current can flow through the leads, causing resistive heating. The wires of the heater may form any number of patterns or paths along the article, depending on the desired area to be heated by the heater. For example, in some cases, the wire is relatively straight along the region of the article that may not require substantial heating, but forms, for example, a serpentine pattern near the region desired to be substantially heated (e.g., in some cases, near a current collector bridge where a heater is used to actively induce thermally-induced volumetric changes in the substrate).

In embodiments where the heater comprises a wire, the heater may comprise any of a number of suitable materials having sufficient resistivity to cause the desired heating of the article. For example, in some cases, the heater comprising a wire comprises a metal and/or metal alloy. As described above, for heaters including thin films, the conductive wire may include a resistive metal or a resistive metal alloy. Examples of materials for the wire of the heater include, but are not limited to, nickel alloys (e.g., nichrome, constantan, alvim (Evanohm), etc.), stainless steel, graphite, silicon-based compounds, combinations thereof, and the like. As described above, the material for the heater including the wire may be selected so as to achieve a desired resistance for the heater.

In some cases, the resistance of a heater (e.g., a heater comprising a film or a heater comprising a wire) may be determined using equation 2:

where R is the resistance of the heater, ρ is the resistivity of the material from which the heater is made, L is the length of the heater in the direction of current flow through the heater, and a is the cross-sectional area of the heater through which current flows. As can be seen from equation 2, in some cases, the desired resistance of the heater may be achieved by selecting a material based on its resistivity ρ, where the material has a greater resistivity, resulting in a greater resistance. Additionally, the geometry of the heater may be selected to determine the resistance of the heater. For example, as can be seen from equation 2, a heater having a larger length dimension has a larger resistance (e.g., a longer wire, a film of a larger length dimension in the direction of current flow (e.g., between two power leads)). According to the embodiment satisfying equation 2, the cross-sectional area a through which current flows in the heater is inversely proportional to the resistance. Thus, in embodiments where the heater includes wires, the resistance of the heater may be increased by using thinner wires (e.g., wires having a small diameter or cross-sectional dimension). In some cases where the heater is or includes a thin film, the resistance may be expressed using equation 3:

Where t is the thickness of the film and w is the width of the film in a direction perpendicular to the direction of current flow (e.g., perpendicular to the length dimension). Thus, according to certain embodiments, the geometry of the film, including the thickness and width of the film, may be adjusted during manufacture of the article (e.g., by changing the width of the film or by adjusting the thickness of the film) to adjust the resistance of the heater.

In the case where resistive heating (e.g., joule heating) is used as at least one of the heating mechanisms, the resistance of the heater may be important. As measured in terms of power, the heat generated during resistive heating is generally proportional to the square of the current and linearly proportional to the resistance. Thus, according to some embodiments, a heater with a greater resistance will provide greater heating for a given current through the heater. In some embodiments, the heater has a relatively high resistance. For example, in some cases, the heater has a resistance of greater than or equal to 50 Ω, greater than or equal to 60 Ω, greater than or equal to 75 Ω, greater than or equal to 100 Ω, greater than or equal to 125 Ω, greater than or equal to 150 Ω, greater than or equal to 200 Ω, and/or up to 300 Ω, up to 400 Ω, up to 500 Ω, up to 1000 Ω, or more at room temperature (23 ℃). Combinations of the above ranges are possible. For example, in some cases, the heater has a resistance greater than or equal to 50 Ω and less than or equal to 1000 Ω.

In some embodiments, the heater is electrically isolated (e.g., not electrically coupled) from certain other components of the article and/or components of the electrochemical device comprising the article. For example, in some cases, the heater is not electronically coupled to the plurality of discrete electrode segments. Electronically isolating the heater from the discrete electrode segments can prevent electrical current from passing through the heater during charging and/or discharging from electronically interfering with electrochemical operation of an electrochemical device including the article, and similarly can prevent electrical current from passing through the heater from electronically interfering with electrochemical operation of the electrochemical device. In some embodiments, the heater is not electronically coupled to the current collector domain. According to certain embodiments, not electronically coupling the heater to the current collector domain (e.g., current collector domain 121) may also avoid interference with the operation and performance of the electrochemical device comprising the article.

The electrical coupling of the heater to the plurality of discrete electrode segments and/or current collector domains of the article may be prevented via various methods. For example, the heater may be placed at the end of the article and physically separated from the discrete electrode segments and current collector domains, as shown in fig. 7B. In some embodiments (e.g., in embodiments in which the heater is integrated into the interior of the article, as shown in fig. 7A), the heater may be prevented from being electrically coupled to the discrete electrode segments and/or current collector domains by incorporating one or more intermediate layers between the heater and the discrete electrode segments and/or current collector domains. In some embodiments, at least a portion of the heater is coated with an electrically insulating material. For example, the heater may be coated with an electrically insulating polymer coating over some or all of the heaters so that the heaters are not in direct contact with the current collector domains or discrete electrode segments. In some cases, a coating (e.g., a protective polymeric coating) is applied to a heater (e.g., a thin film heater or a heater comprising wires) such that the heater is physically isolated from the electrolyte in instances in which the article is incorporated into an electrochemical device.

In some cases, the heater is electrically coupled to an external circuit. For example, according to some embodiments, the heater may be coupled to external circuitry corresponding to the battery control system and management circuitry (e.g., via power leads in contact with the heater). According to certain embodiments, the battery control system may initiate application of current to the heater (e.g., by applying a voltage) upon receiving certain signals or readings of battery conditions (e.g., temperature, current, pressure, etc.) such that the heater heats at least a portion of the article. In some cases, the heater is configured to be actuated by one or more sensors, described in more detail below. For example, the heater may be electronically coupled to battery control and management circuitry configured to receive signals from one or more sensors adjacent to the substrate of the article. One or more sensors may be configured to send a signal to the battery control system (e.g., when the temperature is above a temperature threshold or the pressure is below a pressure threshold), which in turn may send a signal to the sensor that activates the heater to start, stop, or adjust the heater heating.

In some embodiments, an article described herein comprises one or more sensors. In some cases, one or more sensors are adjacent to the substrate of the article. According to certain embodiments, sensors incorporated into articles may be used to monitor the state or performance of the article, for example in cases where the article is part of an electrochemical device (e.g., a battery). The one or more sensors allow, at least in part, detection of a condition (e.g., temperature, pressure) of the electrochemical device. In some cases, one or more sensors adjacent to the substrate are configured to respond to a condition of the article. Fig. 8A depicts an exemplary article 100 including a sensor 160 configured to respond to a condition (e.g., temperature, pressure) of the article 100. It should be understood that while in some cases one or more sensors are in close proximity to a substrate (e.g., directly attached, coated, or vacuum deposited on a substrate without intervening layers or structures between the one or more sensors and the substrate, as shown in fig. 8A and 8B), in some cases the sensors are disposed directly on one or more components (e.g., layers) of the article that are not the substrate. Fig. 8A illustrates a plurality of sensors 160, each sensor 160 being proximate to (but not in direct contact with) a discrete electrode segment and/or a discrete current collector segment, according to some embodiments. In some embodiments, the distance between the heater and the substrate is less than or equal to 5mm, less than or equal to 3mm, less than or equal to 2mm, less than or equal to 1mm, less than or equal to 0.5mm, less than or equal to 0.2mm, less than or equal to 0.1mm, or less.

As in the case of the heaters described above, in some cases, one or more sensors replace (i.e., "replace") components of one or more discrete electrode segments and/or current collector domains in the article structure. For example, in the case where discrete current collector segments are deposited at periodic locations along the substrate during manufacturing (e.g., via a jump coating process), one or more of the locations may be masked so that current collector segments are not deposited there, and in a later step, the sensor is placed at the one or more locations (e.g., after a de-masking step).

In some embodiments, the one or more sensors are located near one or more of the ends of the article. For example, in some, but not necessarily all cases, no discrete electrode or current collector segment is located between one or more sensors and an end of the substrate (with reference to the end according to the long axis of the substrate). For example, FIG. 8B shows a non-limiting embodiment in which the sensor 160 is positioned near an end of the article 100 rather than an internal location such as shown in the illustration of FIG. 8A. According to some, but not necessarily all, embodiments, placing the sensor at or near one of the ends of the article may facilitate ease of manufacturing (e.g., by potentially avoiding complex masking steps) and allow easy access to the sensor even when the article is folded. However, in some cases, placement of one or more sensors in an internal location, such as shown in fig. 8A, may be used to detect and provide local information about the condition of the article (e.g., the temperature or pressure experienced by each discrete electrode segment). As mentioned above and described in more detail below, in some cases, the article is foldable in some embodiments. In some such cases, one or more sensors are positioned between the folded sections of the article when the article is folded. In certain embodiments, such a configuration may allow one or more sensors to readily respond to conditions of internal portions (e.g., folds) of the article and/or an electrochemical device including the folds of the article.

In some embodiments, at least one of the one or more sensors is a temperature sensor configured to respond to a temperature of the article. For example, fig. 8A depicts a sensor 160 adjacent to the substrate 120 of the article 100, according to some embodiments. In some cases, the temperature sensor is capable of measuring a temperature of at least a portion of the article. In some cases, the temperature sensor response (e.g., by sending an electrical signal) varies based on the temperature at the sensor. In some cases, the temperature sensor responds when it detects a temperature above or below some predetermined temperature. According to some, but not necessarily all, embodiments, a temperature sensor incorporated in an article or an electrochemical device including the article allows for detection and/or monitoring of the temperature of substantially the entire article, or in some cases, in the vicinity of individual discrete electrode segments.

The temperature sensor may be any of a number of suitable types of temperature sensors. In some cases, the temperature sensor is or includes a thermocouple. In some cases, the temperature sensor is or includes a thermistor. In some embodiments, the temperature sensor is or includes a Resistance Temperature Detector (RTD). Thermocouples or thermistors may be commercially available and incorporated into articles, for example, or thermocouples may be manufactured and incorporated into articles during the manufacture of the articles themselves. In some, but not necessarily all, embodiments, the temperature sensor is or includes a membrane. In embodiments where a temperature sensor (e.g., thermocouple, thermistor, RTD) is fabricated during the fabrication of an article, the temperature sensor may be formed on a portion of the article (e.g., a substrate or one or more other layers) by any number of suitable methods, such as vacuum deposition methods (e.g., sputtering, evaporation). The temperature sensor may comprise a material having a known resistance versus temperature curve. Examples of materials for the temperature sensor may include, but are not limited to, platinum, nickel, copper, iron, or combinations thereof. In one non-limiting example, the temperature sensor is an RTD that includes a non-conductive layer (ceramic layer) on which a material (e.g., serpentine pattern) having a known resistance versus temperature curve (e.g., platinum, nickel, iron) is deposited. The material having a known resistance versus temperature profile may be electronically coupled to an external circuit (e.g., a computer system and/or a battery control system).

In some embodiments, at least one of the one or more sensors is a pressure sensor. For example, referring again to fig. 8A, according to some embodiments, sensor 160 is a pressure sensor. The pressure sensor may be configured to respond to pressure experienced by the article. In some cases, the pressure sensor is capable of measuring a pressure or force experienced by at least a portion of the article. In some cases, the pressure sensor response (e.g., by sending an electrical signal) varies based on the pressure at the sensor. In some cases, the pressure sensor responds when it detects a pressure above or below some predetermined pressure. According to some, but not necessarily all, embodiments, detecting the pressure experienced by an article or a portion thereof may be used to detect a problem in an electrochemical device including the article (e.g., during cycling of a cell stack) or to determine a risk of damage to the electrochemical device (e.g., in cases where excessive force is applied to the electrochemical device).

The pressure sensor may be any of various types of suitable pressure sensors. In some cases, the pressure sensor is a capacitance-based pressure sensor. One example of a capacitance-based pressure sensor is a pressure sensor that includes two electrodes with an electrically insulating material positioned between the two electrodes. The electrically insulating material may have a known dielectric constant. In some cases, the electrically insulating material is configured such that a force applied to a capacitance-based sensor comprising two electrodes in the electrically insulating material causes a change in the thickness of the electrically insulating material, thereby changing the measured capacitance between the two electrodes. For example, in some cases, the electrically insulating material positioned between the two electrodes is a polymeric material. The polymer material may be relatively soft and have a known dielectric constant. In some cases, the pressure sensor is or includes a strain gauge. In certain embodiments, the pressure sensor comprises a piezoelectric or piezoresistive sensor. Such sensors typically include a piezoelectric or piezoresistive material coupled to an external circuit that is capable of detecting and measuring a change in charge or resistance upon mechanical deformation of the material. In certain embodiments, a pressure sensor Is or includes a film. Non-limiting examples of pressure sensors (e.g., in the form of a membrane) are in f.schmaljohann, d.hagedorn, and F.

"Thin Film Sensors for measuring small Sensors," Journal of Sensors and Sensor systems.No.4, (Feb.2015), 91-95. In some cases, the pressure sensor may be commercially available and attached or coupled to the article or electrochemical device comprising the article. However, in some cases, pressure sensors (e.g., membrane pressure sensors) are manufactured during the manufacture of the article. In some such cases, the pressure sensor is formed by vacuum deposition, coating and curing (e.g., in the case of polymeric materials), printing (e.g., ink jet printing, screen printing), and/or by a spray process (e.g., an aerosol spray process).

In some embodiments, one or more sensors are electrically isolated (i.e., not electronically coupled) from certain other components of the article and/or components of an electrochemical device comprising the article. For example, in some cases, one or more sensors are not electronically coupled to a plurality of discrete electrode segments. Electrically isolating the one or more sensors from the discrete electrode segments can prevent current from passing through the one or more sensors during charging and/or discharging from interfering with operation of an electrochemical device including the article, and similarly can prevent current from passing through the heater from interfering with operation of the electrochemical device. In some embodiments, the one or more sensors are not electronically coupled to the current collector domain. According to certain embodiments, not electronically coupling one or more sensors to a current collector domain (e.g., current collector domain 121) may also avoid interference with the operation and performance of an electrochemical device including the article.

Electronic coupling of one or more sensors to multiple discrete electrode segments and/or current collector domains of an article may be prevented via various methods. For example, one or more sensors may be placed at the end of the article and physically separated from the discrete electrode segments and current collector domains, as shown in fig. 8B. In some embodiments (e.g., in some embodiments in which one or more sensors are integrated into the interior of the article, as shown in fig. 8A), the heater may be prevented from being electrically coupled to the discrete electrode segments and/or current collector domains by incorporating one or more intermediate layers between the one or more sensors and the discrete electrode segments and/or current collector domains. In some embodiments, at least a portion of one or more sensors are coated with an electrically insulating material. For example, one or more sensors may be coated with an electrically insulating polymer coating over some or all of the one or more sensors such that the one or more sensors are not in direct contact with the current collector domains or discrete electrode segments. In some cases, a coating (e.g., a protective polymer coating) is applied to one or more sensors (e.g., a thin film temperature sensor or a pressure sensor) such that the one or more sensors are physically isolated from the electrolyte in instances in which the article is incorporated into an electrochemical device.

In some cases, the one or more sensors are electrically coupled to an external circuit. For example, according to some embodiments, one or more sensors may be coupled (via power leads in contact with the sensors) to external circuitry corresponding to the battery control system and management circuitry. According to certain embodiments, the battery control system may initiate application of current (e.g., by applying a voltage) to the heater described herein upon receiving certain signals or readings of battery conditions (e.g., from one or more sensors), thereby causing the heater to heat at least a portion of the article. According to certain, but not necessarily many, embodiments, heating at least a portion of an electrochemical device using a heater as part of the electrochemical device may allow for rapid electronic isolation (e.g., thermally induced volumetric changes via a substrate) of problematic discrete electrode segments, due at least in part to signals received in response to one or more sensors as part of the electrochemical device. As another non-limiting example, the battery control system may receive a signal from the pressure sensor indicating that the applied pressure/force to the electrochemical device is below a threshold and send a signal to the pressure applicator to increase the applied pressure when the signal is received.

In some embodiments, the sensors may interact with one or more processors, for example, to execute any of the control schemes described herein. In some embodiments, one or more processors may be used to process signals from the sensors, for example, to perform any of the control schemes described herein. In some embodiments, the battery control system and/or management circuitry may include one or more processors. Examples of suitable processors are described in more detail below.

In some embodiments, the thickness of the collector bus is greater than the thickness of at least one of the collector bridges. For example, as shown in fig. 2B, the collector bus 121 has a thickness dimension shown by thickness 161, while the collector bridge 123 has a thickness dimension shown by thickness 162. According to some embodiments, thickness 161 is greater than thickness 162. Having the current collector bridge have a thickness greater than the thickness of the at least one current collector bridge may, in some cases, allow the current collector bridge to be mechanically more robust than the at least one current collector bridge (e.g., requiring a greater applied force to cause failure). For example, in some cases, changing the volume of the substrate causes both the collector bus and the at least one collector bridge to experience mechanical stress (e.g., stretching, bending). In some cases, the mechanical stress causes the collector bridge to break (e.g., due to ultimate tensile failure), but the collector bus does not break due to its greater thickness. Such a scenario may allow discrete electrode segments coupled to the collector bus via at least one collector bridge to be electrically isolated upon a change in volume of the substrate without the collector bus itself failing. In some such cases, an electrochemical device including such an article may still be charged and/or discharged following a loss of electronic coupling between at least one of the electrode segments and the current collector bus. Additionally, a collector bus having a relatively large thickness may allow for reduced resistance and increased current carrying capacity for the entire collector field.

In some embodiments, the thickness of the current collector bus is at least three times, at least four times, at least 5 times, at least 8 times, at least 10 times, at least 20 times, and/or up to 50 times, up to 75 times, or up to 100 times greater than the thickness of at least one of the current collector bridges.

In some embodiments, one or more components of the current collector domain are part of a unitary structure. For example, in some embodiments, the collector bus and the plurality of collector segments are part of a unitary structure. Two or more components are part of a unitary structure if the components are formed of the same material or a consistent combination of materials (e.g., a single metal alloy) and are not fractured. In other words, the unitary structure is a single piece made of a single material or a consistent combination of materials, rather than multiple pieces in contact with each other. For example, referring to fig. 2A, in certain embodiments, the collector bus 121 and the plurality of collector segments, including the collector segment 122, are part of a unitary structure. In some cases, the entire current collector domain forms a unitary structure. Referring to fig. 2A and 2B, although the collector bus 121, the collector segment 122, and the collector bridge 123 associated with the collector segment 122 are shown as three separate components, in certain embodiments, the collector bus 121, the collector segment 122, and the collector bridge 123 form a unitary structure (e.g., a unitary structure of copper metal or copper alloy). In some cases, each collector segment and the collector bridge associated with the collector segment are part of a unitary structure. Forming one or more components of the collector field, such as the collector bus, the plurality of collector segments, and the collector bridge associated with the collector segments, as a unitary structure can simplify manufacture of the article. For example, having the collector bus and the plurality of collector segments as part of a unitary structure may eliminate certain manufacturing steps (e.g., by allowing for the simultaneous manufacturing of the collector bridge and the collector segments).

In some embodiments, the article is configured such that above a threshold current (e.g., a discharge current or a charge current through the collector domain), at least one of the collector bridges is mechanically deformed. In some cases, mechanical deformation may be caused by melting of the current collector bridge (e.g., resistive heating). In some cases, the collector bridge is mechanically deformed due to thermal shock caused by the current reaching a threshold current. In some embodiments, at least one collector bridge is mechanically deformed such that a collector segment that is electronically coupled to that collector bridge is no longer electronically coupled to the collector bus. According to some embodiments, such a situation may occur when the collector bridge is configured to "blow" due to an excessive current (i.e., a current above a threshold current) such that the flow path of the current along the collector bridge is interrupted.

A threshold current as referred to herein is a current that, when the threshold current is reached (e.g., due to a short circuit), causes mechanical deformation of at least one collector bridge such that the collector segment associated with that collector bridge becomes decoupled from the collector bus. In some embodiments, the article is configured such that the threshold current referred to herein falls within a particular range of current. For example, the article can be configured such that the threshold current is sufficiently high such that loss of electronic coupling (e.g., due to mechanical deformation) between the collector bridge and the collector bus does not occur during normal operation of an electrochemical device including the article (e.g., normal charging and/or discharging without short circuiting or thermal runaway). Thus, in certain embodiments, the article may be configured such that the threshold current of the article is greater than or equal to 10A. It should be understood that a threshold current of the article falling within a particular range of currents means that a particular current of the article configured to undergo at least one electronic decoupling as described herein upon mechanical deformation of the at least one current collector bridge falls within that range. An article configured to have a threshold current of 100A is one example for an article whose threshold current is greater than or equal to 10A because 100A falls within a range of values greater than or equal to 10A.

In some embodiments, the article may be configured such that the threshold current is sufficiently low such that a loss of electronic coupling between the collector segment and the collector bus occurs at a sufficiently low current such that no significant damage to the article and/or an electrochemical device comprising the article occurs prior to the loss of coupling. Thus, in certain embodiments, the article may be configured such that the threshold current of the article is less than 120A or 120A. As another non-limiting example, an article configured to have a threshold current of 90A is an article for which the threshold current is less than or equal to 120A because 90A falls within a range of values less than or equal to 120A.

In some embodiments, one or more components of the articles and systems described herein are continuous structures. "continuous" as used to describe the relationship between two sections, layers or portions of a structure means that there is at least one path from a first section, layer or portion to a second section, layer or portion that passes only through the structure. For example, a continuous sheet of material folded upon itself or around a different material may define two or more sections or portions that remain part of the continuous sheet because there is at least one path through the sheet from a first section to a second section only (e.g., a path that travels from the first section along and around a crease and to the second section). Referring to fig. 10A through 10B, the first anode portion 431, the second anode portion 432, and the folded anode region 435 of the electrochemical device 400B are sections of a structure (e.g., an anode), and the structure is continuous with respect to the first anode portion 431 and the second anode portion 432 because there is a path from the first anode portion 431 through the folded anode region 435 and to the second anode portion 432 through only the structure including the first anode portion 431, the second anode portion 432, and the folded anode region 435. In contrast, referring to fig. 9A-9B, the first anode portion 431 and the second anode portion 432 of the electrochemical device 400A are discontinuous because any path from the first anode portion 431 to the second anode portion 432 must pass through at least one structure (e.g., the separator 450, the first cathode portion 531, the gap 405) that does not include the first anode portion 431 and the second anode portion 432.

In some embodiments, the current collector bus is a continuous layer. For example, referring to fig. 1, the current collector bus 121 is a continuous layer, rather than being formed from multiple discrete layers or segments. Having a continuous collector bus may be useful for various reasons. For example, due to the continuous conductive path, a loss of electrical connection (e.g., due to a fault) between the collector bus at one section of the collector bus and a component of the external circuit (e.g., an electrode tab) does not necessarily disrupt the electronic coupling between the collector bus at that section and other components of the external circuit that form electrical connections at other sections of the collector bus. For example, referring to fig. 1, according to certain embodiments, electrical connections to external components, such as electrode tabs, are made at

sections

203 and 205 of the collector bus 121. The current generated at the discrete electrode segment 130a may be transferred to an external component at segment 203 or segment 205 of the collector bus 121. Because the collector bus 121 is continuous, loss of electrical connection between the collector bus 121 and an external component at the segment 203 does not prevent the current generated at the discrete electrode segment 130a from passing to an external circuit because the discrete electrode segment 130a is still electrically coupled to the collector bus 121 at the segment 205.

Other components of the articles and systems described herein may also be continuous, as described above. For example, the substrate of the article may be continuous. Referring to fig. 1, according to some embodiments, any two sections of the substrate 120 are continuous. Having a continuous substrate may allow for simplified manufacture of the articles and multi-cell batteries described herein. For example, when the substrate is continuous, the articles described herein can be made by: by attaching (e.g., via coating or deposition) the current collector domain and the plurality of discrete electrode segments onto a single continuous substrate, rather than having to separately fabricate the discrete electrode segments, substrate segments, and/or components of the current collector domain and then attach them (e.g., to form an article or a cell stack). Other components of the systems described herein that may be continuous include, but are not limited to, the separator and/or the second electrode of the electrochemical device comprising the article, as described in more detail below.

The articles described herein may be manufactured according to any suitable method. In some cases where the substrate is continuous, the current collector domains and/or discrete electrodes are formed on the substrate. Non-limiting examples of techniques that may be used to form the current collector domains (including the current collector bus and optional current collector segments and the current collector bridge) and the plurality of discrete electrode segments include coating and deposition methods such as casting, evaporation deposition, vacuum deposition, or spin coating. One non-limiting example of a suitable vacuum deposition is sputtering.

One exemplary but non-limiting method of forming an article involves starting with a substrate that includes a release layer comprising a suitable material (e.g., polyvinyl alcohol). The mask may then be patterned onto the substrate such that when a thin layer of metal (e.g., copper) is coated onto the substrate, areas of the substrate (i.e., voids/gaps) are not directly coated with the metal. After the metal is coated to form at least a portion of the current collector region, an electrode active material (e.g., lithium and/or lithium alloy) may be coated or deposited on the metal layer (e.g., on the region of the metal layer corresponding to the current collector segment). According to certain embodiments, the substrate is subsequently peeled from the mask material to yield the articles described herein. In some cases, the patterning of the mask on the substrate is designed such that the metal-coated regions correspond to the current collector bridge, and in some cases, the metal (e.g., copper metal) is continuously deposited and has a greater thickness at the edges of the article to create a current collector bus having an increased thickness relative to other components of the current collector domain.

The use of a continuous substrate and/or a continuous current collector bus in the manufacture of a multi-cell battery can avoid the laborious steps associated with manufacturing cells having a stacked arrangement, resulting in a faster, easier, and less expensive manufacturing process. For example, having a continuous substrate (e.g., a release layer) on which other components of the article (e.g., the current collector region and the plurality of discrete electrode segments) can be deposited or coated eliminates the need to cut separate lamination units, arrange them, and make a large number of external electrical contacts.

In some embodiments, the article may be folded. The folded article may be particularly useful when one or more components (e.g., substrate, current collector bus) are continuous. Fig. 2C shows a schematic side view of an unfolded article 100 including a continuous substrate 120 (e.g., before folding). Fig. 5 shows a schematic side view of an article 100 that is partially folded (with a full fold involving folding according to the two block arrows shown in fig. 5) according to some embodiments. It should be noted that the current collector bus 121 has been omitted from the article 100 in fig. 5 for clarity. Folding the article may involve folding the substrate at the interstices/gaps between the discrete electrode segments and/or current collector segments. Referring again to fig. 5, the substrate 120 is folded at the gaps between each of the plurality of collector segments including collector segment 122. When the article is folded in this manner, a "double-sided" electrode is formed, each side of the double-sided electrode comprising a discrete electrode segment (e.g., a discrete electrode segment from the plurality of discrete electrode segments 130). The use of double-sided electrodes may provide a battery with a relatively high volumetric energy density, which may be desirable in many applications.

In another aspect, an electrochemical device is described. In some embodiments, an electrochemical device comprises at least one anode and at least one cathode. It should be understood that although the article including the current collector bus and the plurality of discrete electrode segments described above may be included in a folded electrochemical device, other electrode geometries and configurations may be used in a folded electrochemical device. In some cases, the electrochemical device includes a separator (e.g., a continuous or serpentine separator). In some cases, the electrochemical device may be used as a battery (e.g., a multi-cell battery such as a rechargeable lithium battery). As mentioned above, in some cases, the electrochemical device is folded. In some, but not necessarily all cases, folded electrochemical cells are easier and/or more economical to produce and can have relatively high volumetric energy densities, as compared to electrochemical devices formed with stacked designs rather than folded designs.

In some embodiments, an electrochemical device includes a plurality of electrode portions. For example, in some embodiments, an electrochemical device includes a plurality of anode portions. Each anode portion of the electrochemical device may include an anode active surface portion. In some cases, an electrochemical device comprises: a first anode portion comprising a first anode active surface portion; a second anode portion comprising a second anode active surface portion; a third anode portion comprising a third anode active surface portion; and a fourth anode portion comprising a fourth anode active surface portion. In certain embodiments, each of the first anode portion, the second anode portion, the third anode portion, and the fourth anode portion includes lithium and/or a lithium alloy as an anode active material.

In some embodiments, at least some of the anode portions of the electrochemical device are discrete (e.g., discrete electrodes). For example, in some cases, each of the first anode portion, the second anode portion, the third anode portion, and the fourth anode portion is discrete. Referring to fig. 9A, fig. 9A shows a schematic cross-sectional view of a partially expanded electrochemical device for clarity, the electrochemical device 400A comprising: a first anode part 431, the first anode part 431 comprising a first anode active surface part 441; a second anode portion 432, the second anode portion 432 including a second anode active surface portion 442; a third anode portion 433, the third anode portion 433 including a third anode active surface portion 443; and a fourth anode portion 434, the fourth anode portion 434 including a fourth anode active surface portion 444. According to some embodiments of the electrochemical device 400A in fig. 9A, each of the first anode portion 431, the second anode portion 432, the third anode portion 433, and the fourth anode portion 434 is discrete. In some cases, such discrete anode portions may be fabricated via jump coating or using deposition techniques (e.g., evaporative deposition, vacuum deposition such as sputtering) in conjunction with one or more masks.

In some embodiments, an electrochemical device (e.g., a folded electrochemical device) includes a continuous anode. For example, referring to fig. 10A, electrochemical device 400B includes a continuous anode 430. The anode portion of the electrochemical device may be a portion of a continuous anode. For example, in certain embodiments, the first anode portion, the second anode portion, the third anode portion, and the fourth anode portion are part of a continuous anode. Referring to fig. 10B, the first anode portion 431, the second anode portion 432, the third anode portion 433, and the fourth anode portion 434 are each a part of the continuous anode 430. As mentioned above, the first anode portion 431 and the second anode portion 432 are part of the continuous anode 430 at least because there is a path (e.g., via the folded anode region 435) between the first anode portion 431 and the second anode portion 432 that is part of a structure (e.g., an anode) that includes the first anode portion 431 and the second anode portion 432. As noted above, in some, but not necessarily all cases, a continuous electrode (e.g., a continuous anode) may provide a folded electrochemical device (e.g., a multi-cell battery) for relatively easy and inexpensive manufacture and establishment of electrical connections.

In some cases, the distinction between anode portions (e.g., first anode portion, second anode portion, etc.) of an electrochemical device may be established by a fold in the electrochemical device. For example, in some cases, at least a portion of the continuous anode is folded to establish a section of the anode (e.g., a first anode portion) on one side of the fold and a section of the anode (e.g., a second anode portion) on the other side of the fold. In other cases, the distinction between the anode portions of an electrochemical device is established by the anode portions being discrete anode portions. In some such cases, the discrete anode portions are located in folded-apart sections of the electrochemical device.

In some embodiments, active surface portions of certain anode portions of folded electrochemical cells face each other. For example, in some cases, the second anode surface portion faces the first anode active surface portion. Fig. 9B depicts a cross-sectional view of an exemplary electrochemical device 400A in which the second anode active surface portion 442 faces the first anode active surface portion 441, according to some embodiments. In some cases, the fourth anode active surface portion faces both the first anode active surface portion and the third anode active surface portion. In some such cases, the third anode portion is positioned at least partially between the first anode portion and the fourth anode portion. Fig. 9B shows an embodiment of an electrochemical device 400A in which a third anode portion 433 is positioned at least partially between the first and

fourth anode portions

431, 434, and in which a fourth anode active surface portion 444 faces both the first and third anode

active surface portions

441, 443.

As used herein, a surface (or surface portion) is considered to "face" an object when the surface and the object intersect the object substantially parallel and perpendicular to and away from a line that includes a majority of the material of the surface. For example, the first surface (or first surface portion) and the second surface (or second surface portion) may face each other if a line perpendicular to the first surface and extending away from a majority of the material comprising the first surface intersects the second surface. A surface and a layer may face each other if a line perpendicular to the surface and extending away from a majority of material comprising the surface intersects the layer. The surface may face another object when the surface is in contact with the other object, or when one or more intermediate materials are positioned between the surface and the other object. For example, two surfaces facing each other may be in contact or may include one or more intermediate materials therebetween.

In some cases, active surface portions of certain anode portions of the folded electrochemical device face away from each other. For example, in some cases, the third anode active surface portion faces away from both the first anode active surface portion and the second anode active surface portion. Fig. 9B depicts a third anode active surface portion 443, which third anode active surface portion 443 faces away from both the first anode active surface portion 441 and the second anode active surface portion 442.

As used herein, a surface (or portion of a surface) is considered to be "facing away" from an object when the surface and the object are substantially parallel and do not intersect the object along a line extending perpendicular to and away from a majority of the material comprising the surface. For example, the first surface (or first surface portion) and the second surface (or second surface portion) may face away from each other if no line extending perpendicular to the first surface and away from a majority of the material comprising the first surface intersects the second surface. A surface and a layer may face away from each other if no line extending perpendicular to the surface and away from a majority of material comprising the surface intersects the layer. In some embodiments, a surface and another object (e.g., another surface, layer, etc.) may be substantially parallel if the maximum angle defined by the surface and the object is less than about 10 °, less than about 5 °, less than about 2 °, or less than about 1 °.

In some embodiments, the electrochemical device comprises a plurality of cathode portions. Each cathode portion of the electrochemical device may include a cathode active surface portion. In some cases, an electrochemical device comprises: a first cathode portion comprising a first cathode active surface portion; a second cathode portion comprising a second cathode active surface portion; a third cathode portion comprising a third cathode active surface portion; and a fourth cathode portion comprising a fourth cathode active surface portion.

In some embodiments, at least some of the cathode portions of the electrochemical device are discrete (e.g., discrete electrodes). For example, in some cases, each of the first cathode portion, the second cathode portion, the third cathode portion, and the fourth cathode portion is discrete. Referring to fig. 9A, an electrochemical device 400A includes: a first cathode portion 531, the first cathode portion 531 comprising a first cathode active surface portion 541; a second cathode portion 532, the second cathode portion 532 comprising a second cathode active surface portion 542; a third cathode portion 533, the third cathode portion 533 including a third cathode active surface portion 543; and a fourth cathode portion 534, the fourth cathode portion 534 including a fourth cathode active surface portion 544. According to some embodiments of the electrochemical device 400A in fig. 9A, each of the first cathode portion 531, the second cathode portion 532, the third cathode portion 533, and the fourth cathode portion 534 is discrete. Such discrete cathode portions may be fabricated using any suitable method, for example, via jump coating or using a deposition technique incorporating one or more masks (e.g., evaporative deposition, vacuum deposition such as sputtering).

In some embodiments, an electrochemical device (e.g., a folded electrochemical device) includes a continuous cathode. The cathode portion of the electrochemical device may be part of a continuous cathode. For example, in certain embodiments, the first cathode portion, the second cathode portion, the third cathode portion, and the fourth cathode portion are part of a continuous cathode. Although not explicitly shown in fig. 9A-10B, according to some embodiments, the first cathode portion 531, the second cathode portion 532, the third cathode portion 533, and the fourth cathode portion 544 may be part of a continuous cathode.

As with the anode portion described above, in some cases, the distinction between the cathode portions of the electrochemical device may be established by folds in the electrochemical device. For example, in some cases, at least a portion of the continuous cathode is folded to establish a section of the cathode (e.g., a first cathode portion) on one side of the fold and a section of the cathode (e.g., a second cathode portion) on the other side of the fold. In other cases, the distinction between the cathode portions of an electrochemical device is established by the cathode portions being discrete cathode portions. In some such cases, the discrete cathode portions are located in folded-apart sections of the electrochemical device.

In some embodiments, two electrode portions may be arranged to form a double-sided electrode having a first side and a second side opposite the first side, both sides comprising an electrode active material and an active surface. For example, in some cases, a folded electrochemical device described herein can include a double-sided cathode. One non-limiting example is an electrochemical device comprising a first cathode portion and a second cathode portion, wherein the first cathode portion forms at least a portion of a first side of a double-sided cathode and the second cathode portion forms at least a portion of a second side of the double-sided cathode. Such an arrangement is possible in the case where the first cathode portion and the second cathode portion are separate cathodes, or in the case where the first cathode portion and the second cathode portion are part of a continuous cathode. Referring to fig. 9B, for example, according to some embodiments, the first cathode portion 531 and the second cathode portion 532 form a double-sided cathode 530, the double-sided cathode 530 comprising a first cathode active surface portion 541 facing away from a second cathode active surface portion 542.

In some embodiments, the active surface portions of certain cathode portions of the folded electrochemical cell face certain anode active surface portions. For example, in some cases, the first cathode active surface portion faces the first anode active surface portion. Fig. 9B and 10B depict cross-sectional views of an exemplary electrochemical device 400A and an exemplary electrochemical device 400B, respectively, according to certain embodiments, wherein the first cathode active surface portion 541 faces the first anode active surface portion 441. In some cases, the second cathode active surface portion faces the second anode active surface portion, the third cathode active surface portion faces the third anode active surface portion, and the fourth cathode active surface portion faces the fourth anode active surface portion. In some, but not necessarily all cases, facing respective cathode and anode active surface portions as described herein to each other results in a folded electrochemical device that is capable of including multiple electrochemical cells (e.g., upon addition of an electrolyte) in a relatively easy to manufacture and volumetrically energy-dense configuration.

As mentioned above and described in more detail below, in some embodiments, the electrochemical device includes a separator. For example, fig. 9A-9B and 10A-10B depict an example electrochemical device 400A and an example electrochemical device 400B, respectively, each of the example electrochemical device 400A and the example electrochemical device 400B including a separator 450. In some cases, such as in embodiments where the electrochemical device is folded, the separator is also folded. In some cases, the separator is arranged such that the first portion of the separator is between the first anode portion and the first cathode portion. For example, referring to fig. 9B, the first portion 451 of the separator 450 is between the first anode portion 431 and the first cathode portion 531. In some cases, the separator is arranged such that the separator is positioned between the plurality of anode portions and the cathode portion. For example, in some embodiments, the separator is arranged such that a first portion of the separator is between the first anode portion and the first cathode portion, a second portion of the separator is between the second anode portion and the second cathode portion, a third portion of the separator is between the third anode portion and the third cathode portion, and a fourth portion of the separator is between the fourth anode portion and the fourth cathode portion. For example, referring to fig. 9B, the first portion 451 of the separator 450 is between the first anode portion 431 and the first cathode portion 531, the second portion 452 of the separator 450 is between the second anode portion 432 and the second cathode portion 532, the third portion 453 of the separator 450 is between the third anode portion 433 and the third cathode portion 533, and the fourth portion 454 of the separator 450 is between the fourth anode portion 434 and the fourth cathode portion 534. Such an arrangement is also depicted in electrochemical device 400B of fig. 10B, which includes a continuous anode 430. In some cases, the separator of the electrochemical device may be a serpentine separator. For example, according to some embodiments, the spacer 450 in fig. 9B is a serpentine spacer. In some, but not necessarily all, embodiments, serpentine separators and other continuous separators can provide relatively easy to manufacture and efficient means in folded electrochemical devices to provide electrically insulating but ionically conductive paths for electrochemical reactions while preventing problems such as short circuits.

In some embodiments, an electrochemical device described herein comprises components arranged in a particular order. For example, an electrochemical device may include a plurality of anode portions, a plurality of cathode portions, and a separator (e.g., a serpentine separator), wherein the electrochemical device includes the following arranged in the following order: a first anode portion comprising a first anode active surface portion; a first spacer portion; a first cathode portion comprising a first cathode active surface portion; a second cathode portion comprising a second cathode active surface portion; a second spacer portion; a second anode portion comprising a second anode active surface portion; a third anode portion comprising a third anode active surface portion; a third spacer portion; a third cathode portion comprising a third cathode active surface portion; a fourth cathode portion comprising a fourth cathode active surface portion; a fourth spacer portion; and a fourth anode portion comprising a fourth anode active surface portion. Fig. 9B and 10B illustrate an exemplary electrochemical device 400A and an exemplary electrochemical device 400B, respectively, each of the exemplary electrochemical device 400A and the exemplary electrochemical device 400B including such components arranged in such an order. Specifically, in fig. 9B, from the left side of the figure to the right side of the figure, the electrochemical device 400A includes the following arranged in the following order: a first anode part 431, the first anode part 431 comprising a first anode active surface part 441; a first spacer portion 451; a first cathode portion 531, the first cathode portion 531 comprising a first cathode active surface portion 541; a second cathode portion 532, the second cathode portion 532 comprising a second cathode active surface portion 542; a second spacer portion 452; a second anode portion 432, the second anode portion 432 including a second anode active surface portion 442; a third anode portion 433, the third anode portion 433 including a third anode active surface portion 443; the third spacer portion 453; a third cathode portion 533, the third cathode portion 533 including a third cathode active surface portion 543; a fourth cathode portion 534, the fourth cathode portion 534 including a fourth cathode active surface portion 544; a fourth spacer portion 454; and a fourth anode portion 434, the fourth anode portion 434 including a fourth anode active surface portion 444.

As described above and in more detail below, in some, but not necessarily all, cases, an electrochemical device includes a substrate. For example, in some cases, one or more electrodes are formed on a substrate (optionally with one or more intermediate layers, such as current collectors). In some cases, one or more of the plurality of anodes are formed on the substrate. Referring again to fig. 9A, according to some embodiments, the exemplary electrochemical device 400A includes a substrate 420. In some, but not necessarily all, embodiments, the substrate is adjacent to one or more of the plurality of anode portions. For example, in some cases, an electrochemical device includes a substrate adjacent to each of a first anode portion, a second anode portion, a third anode portion, and a fourth anode portion. Referring again to fig. 9B, the substrate 420 is adjacent to each of the first, second, third, and

fourth anode portions

431, 432, 433, and 434. In certain embodiments, the substrate of the electrochemical device is continuous. For example, the substrate 420 in fig. 9A may be a continuous sheet including a polymer (e.g., a release layer) on which one or more components of the electrochemical device, such as a current collector (e.g., a current collector region) and/or a first anode portion 431, a second anode portion 432, a third anode portion 433, and a fourth anode portion 434 are formed. In some embodiments, the substrate (e.g., substrate 420) is or includes a release layer, as described in more detail below. In some cases, the substrate or a portion of the substrate is positioned between certain components of the electrochemical device when the electrochemical device is folded. In some cases, a portion of the substrate is between the second anode portion and the third anode portion. For example, in the folded electrochemical device 400A of fig. 9B or the folded electrochemical device 400B of fig. 10B, the substrate portion 421 is between the second anode portion 432 and the third anode portion 433.

The electrochemical devices described herein (e.g., folded electrochemical devices) can include one or more current collectors, as mentioned above. In some cases, the electrochemical device includes an anode current collector. The anode current collector may be electronically coupled to the anode and/or the plurality of anode portions of the electrochemical device. In some cases, each of the anode portions of the electrochemical device is electronically coupled to a different current collector (e.g., a different discrete current collector). However, in some cases, the electrochemical device includes an anode current collector electrically coupled to each of the first, second, third, and fourth anode portions. Each of fig. 9A-9B and 10B depicts an electrochemical device including an anode current collector 425. In some cases, the anode current collector 425 is electrically coupled to each of the first anode portion 431, the second anode portion 432, the third anode portion 433, and the fourth anode portion 434. In some cases, such an anode current collector is a continuous anode current collector. For example, the anode current collector 425 in fig. 9A-9B and 10A-10B may be continuous, according to some embodiments. While certain specific current collector configurations are described in this disclosure (e.g., including a current collector field having multiple current collector segments and a current collector bridge), it should be understood that an anode current collector may include other configurations in certain circumstances. For example, in some cases, the anode current collector is a layer of electronically conductive material, a portion of which is adjacent (e.g., directly adjacent or with one or more intervening layers) to the first, second, third, and fourth anode portions.

In some embodiments, the electrochemical device comprises a plurality of cathode current collectors and/or cathode current collector portions. As one non-limiting example, an electrochemical device may include a first cathode current collector electronically coupled to a first cathode portion; and a second cathode current collector electronically coupled to the third cathode portion. Referring to fig. 9B, according to some embodiments, electrochemical device 400A includes an optional first cathode current collector portion 524 and an optional second cathode current collector portion 526. In some cases, the first cathode current collector portion and the second cathode current collector portion are part of a continuous cathode current collector. According to some, but not necessarily all, embodiments, the use of such a continuous cathode current collector may provide an easy to manufacture and convenient arrangement to form an electrical connection to the cathode portion of the folded electrochemical device, as in the case of other continuous components described above and below. While first cathode current collector portion 524 and second cathode current collector portion 526 are not shown as part of a continuous cathode current collector in fig. 9B and 10B, it should be understood that in some, but not necessarily all embodiments, first current collector portion 524 and second cathode current collector portion 526 are part of a continuous cathode current collector. For example, fig. 9A and 10A, depicting a partially expanded electrochemical device 400A and electrochemical device 400B, respectively, show a continuous cathode current collector 525, according to certain embodiments. However, in some cases, the first cathode current collector portion and the second cathode current collector portion are separate. For example, in some, but not necessarily all embodiments, first cathode current collector portion 524 and second cathode current collector portion 526 are separate current collectors. In some cases, the electrochemical device includes a first cathode current collector electronically coupled to the first cathode portion; and a second cathode current collector electronically coupled to the third cathode portion. For example, according to some embodiments, the first current collector portion 524 is electronically coupled to the first cathode portion 531, and the second cathode current collector 526 is electronically coupled to the third cathode portion 533.

While certain electrochemical devices described and illustrated herein are described using a particular number of components (e.g., four anode portions and four cathode portions), it should be understood that the number of components described herein is non-limiting. For example, the electrochemical device may comprise a fifth (or sixth or more) anode portion comprising a fifth (or sixth or more) anode active surface portion and a fifth (or sixth or more) cathode portion comprising a fifth (or sixth or more) cathode active surface portion facing the fifth (or sixth or more) anode active surface portion. Additionally, although the electrochemical device is shown as "W" shaped folds (e.g., having three folds), in some cases the electrochemical device may include additional folds (as well as additional anode and cathode portions). For example, in some embodiments, the electrochemical device has at least 3 folds, at least 4 folds, at least 5 folds, at least 10 folds, and/or up to 12 folds, up to 15 folds, up to 20 folds, or more.

In certain embodiments, electrochemical devices (e.g., folded electrochemical devices) are constructed and arranged to avoid problems associated with the use of certain anode active materials or certain geometries. As a non-limiting example, one or more anodes of an electrochemical device may include lithium and/or a lithium alloy as an anode active material, which may form dendrites under certain conditions. As another non-limiting example, one or more anodes of an electrochemical device may be subject to uneven utilization or over-utilization in certain areas of the anode. In some cases, the size and/or orientation of the anode (e.g., the anode portion) is configured to address some such issues (e.g., uneven utilization or over-utilization in certain areas).

One such way to avoid certain problems associated with certain anode materials is to use an "oversized" anode (or anodes) relative to the cathode of the electrochemical device. For certain electrochemical devices described herein (e.g., folded electrochemical devices), an "oversized" anode is achieved by configuring the electrochemical device such that a relatively high percentage of the perimeter of the cathode (e.g., cathode portion) is covered by the anode active surface. Specifically, in some embodiments, the electrochemical device includes a cumulative cathode active surface perimeter defined by a sum of perimeters of all cathode active surfaces of the electrochemical device. In the case where the plurality of cathode portions are discrete, the cumulative cathode active surface perimeter of the electrochemical device is defined by the sum of the perimeters of the cathode active surfaces of each of the cathode portions. For example, referring to fig. 11A, if the only cathodes of the exemplary electrochemical device are a discrete cathode portion 650 having a cathode active surface 655, a discrete cathode portion 660 having a cathode active surface 665, and a discrete cathode portion 670 having a cathode active surface 675, the cumulative cathode active surface perimeter of the electrochemical device is the sum of the perimeter of the cathode active surface 655 (i.e., cathode perimeter segment 651 plus cathode perimeter segment 652 plus cathode perimeter segment 653 plus cathode perimeter segment 654), the perimeter of the cathode active perimeter surface 665 (i.e., cathode perimeter segment 661 plus cathode perimeter segment 662 plus cathode perimeter segment 663 plus cathode perimeter segment 664), and the perimeter of the cathode active surface 675 (i.e., cathode perimeter segment 671 plus cathode perimeter segment 672 plus cathode perimeter segment 673 plus cathode perimeter segment 674).

As another example, in the case where the electrochemical device includes a single continuous cathode, the cumulative cathode active surface perimeter of the electrochemical device is the perimeter of the cathode active surface of the continuous cathode. For example, referring to fig. 11B, if the only cathode of the exemplary apparatus is the cathode 680 having a cathode active surface 685, the cumulative cathode active surface perimeter is the sum of the cathode perimeter segment 681, the cathode perimeter segment 682, the cathode perimeter segment 683, and the cathode perimeter segment 684.

In some embodiments, a relatively high percentage of the cumulative cathode active surface perimeter of the electrochemical device is covered by the anode active surface. In some, but not necessarily all cases, such configurations may be used to mitigate certain problems, such as dendrite formation in folded electrochemical devices. A point on the perimeter of the cathode active surface is covered by the anode active surface if, on a line intersecting the point and perpendicular to the cathode perimeter, a point is present inside the cathode perimeter and a point is present outside the cathode perimeter covered by the anode active surface. In other words, if the anode active surface "extends" beyond the cathode active surface perimeter, rather than failing to reach or stopping directly at the cathode active surface perimeter point, a point on the cathode active surface perimeter is covered by the anode active surface.

Fig. 12 depicts a top-down view of the cathode active surface 640 (indicated by gray shading). At least a portion of the cathode active surface 640 faces the anode active surface 740 (indicated by diagonal hatching). In fig. 12, the cathode perimeter segment 632 (which spans from point a to point b) and the cathode perimeter segment 634 (which spans from point e to point f) are covered by the anode active surface 740, respectively, as indicated by the bold black lines. On the other hand, the cathode perimeter section 622 (which spans from point a to point f) is not covered by the anode active surface 740 (as indicated by the thick dashed line) because the anode active surface 740 reaches but does not extend beyond the cathode perimeter section 622. The cathode perimeter section 623 (which spans from point b to point c), the cathode perimeter section 624 (which spans from point c to point d), and the cathode perimeter section 625 (which spans from point d to point e) are not covered by the anode active surface 740 (as also indicated by the thick dashed line), because the anode active surface 740 does not reach the cathode perimeter section 623, the cathode perimeter section 624, or the cathode perimeter section 625. Where the cumulative cathode active surface perimeter of the cathode active surface 640 is defined by the sum of the cathode perimeter section 622, the cathode perimeter section 623, the cathode perimeter section 624, the cathode perimeter section 625, the cathode perimeter section 632, and the cathode perimeter section 634, the percentage of the cumulative cathode active surface perimeter covered by the anode active surface 640 is determined by dividing the sum of the cathode perimeter section 632 and the cathode perimeter section 634 by the cumulative cathode active surface perimeter. In some embodiments, at least 60%, at least 75%, at least 90%, at least 95%, at least 99%, or all of the cumulative cathode active surface perimeter is covered by the anode active surface.

As noted above, in some embodiments, the articles described above (e.g., including the substrate, the current collector bus, the plurality of discrete electrode segments, and optionally the current collector segments and the current collector bridge) are components of an electrochemical device. Fig. 4 shows a schematic of an exemplary electrochemical device 200 including article 100. In some cases, an electrochemical cell (e.g., an electrochemical device comprising an article having a plurality of discrete electrode segments) described herein is a multi-cell structure. For example, in fig. 4, the electrochemical device 200 is a multi-cell structure. Some such electrochemical devices may be used as part of a battery (e.g., a rechargeable lithium ion battery).

The electrochemical device (e.g., comprising an article) can comprise a second electrode. For example, referring again to fig. 4, the electrochemical device 200 includes a second electrode 230. The second electrode may comprise or be made of any suitable electrode active material. In some embodiments, the second electrode has a polarity opposite to the polarity of the plurality of discrete electrode segments. Typically, if one electrode is an anode and the other electrode is a cathode, the two electrodes have opposite polarities. For example, in some cases, the plurality of discrete electrode segments (e.g., the plurality of discrete electrode segments 130) are a plurality of anodes and the second electrode of the electrochemical device (e.g., the second electrode 230) is a cathode. The opposite arrangement is also possible. In some cases, the active surface of the plurality of discrete electrode segments faces the active surface of the second electrode. For example, in fig. 4, the discrete electrode segment 130a includes an active surface 131, the second electrode 230 includes an active surface 231, and the active surface 131 faces the active surface 231.

Electrical contact to the second electrode may be made using any suitable technique. For example, the second electrode may be in electrical contact with a second current collector. Fig. 4 shows a second current collector 225, the second current collector 225 being adjacent to the second electrode 230 and being electronically coupled to the second electrode 230. As with the current collector domains described above, the second current collector may comprise or be made of any suitable electronically conductive material (e.g., an electrically conductive metal such as aluminum). The second current collector may be immediately adjacent to the second electrode (e.g., second current collector 225 may be in direct contact with second electrode 230), or one or more intermediate layers (e.g., an undercoat layer) may be disposed between the second electrode and the second current collector (e.g., to promote adhesion between the second electrode and the second current collector).

As mentioned above, in some embodiments, the electrochemical device includes a separator interposed between the plurality of discrete electrode segments and the second electrode. For example, referring to fig. 4, the electrochemical device 200 includes a separator 250 interposed between the plurality of discrete electrode segments 130 (e.g., the plurality of anodes) and the second electrode 230 (e.g., the cathode). The separator may be a solid non-electronically conductive or electronically insulating material that electrically isolates the anode and cathode from each other to prevent electronic shorting and allow the transport of ions between the anode and cathode. In some embodiments, the separator may be porous and may be permeable to the electrolyte. In some cases, the separator is continuous, which may be useful where one or more of the electrodes (e.g., the second electrode) of the electrochemical device is continuous. For example, fig. 4 shows a diagram of a spacer 250 according to some embodiments, wherein the spacer 250 is depicted as continuous.

The pores of the separator may be partially or substantially filled with an electrolyte. The separator may be provided as a porous, independent membrane that is interleaved with the anode and cathode during the manufacture of the battery. Alternatively, a porous separator layer may be applied directly to the surface of one of the electrodes, for example, as described in PCT publication No. WO 99/33125 to Carlson et al and U.S. patent No. 5194341 to Bagley et al.

A variety of spacer materials are known in the art. Examples of suitable solid porous separator materialsIncluding but not limited to polyolefins such as, for example, polyethylene (e.g., SETELA manufactured by Tonen Chemical Corp)^TM) And polypropylene, glass fiber filter paper and ceramic materials. For example, in some embodiments, the separator comprises a microporous polyethylene film. Other examples of separator and separator materials suitable for use in the electrochemical devices described herein, including electrochemical cells, are those comprising a microporous xerogel layer, such as a microporous pseudo-boehmite layer, which may be provided as a stand-alone film or applied by direct coating on one of the electrodes (e.g., a plurality of discrete electrode segments, a second electrode), as described in commonly assigned us patent nos. 6,153,337 and 6,306,545 to Carlson et al. Solid electrolytes and gel electrolytes can also act as separators in addition to their electrolyte function.

In some embodiments, the electrochemical device comprises a plurality of discrete second electrodes. For example, fig. 6A illustrates a non-limiting embodiment of an electrochemical device 200 comprising a plurality of discrete second electrodes comprising a second electrode 230 (electrically coupled to a second current collector 225) separated from the article 100 by a separator 250. According to certain embodiments, the article 100 in fig. 6A includes a substrate 120, a plurality of discrete electrode segments 130, a plurality of current collector segments including current collector segment 122, and a current collector bridge and bus (not shown). In some cases, the discrete second electrodes are double-sided electrodes (e.g., electrodes having a first side and a second side opposite the first side, both sides including an electrode active material and an active surface). In some embodiments, electrochemical device 200 can be folded in a manner similar to that described above with respect to folding of articles or other exemplary electrochemical devices described herein. For example, referring to fig. 6A, according to certain embodiments, article 100 and separator 250 (e.g., a continuous separator) are folded as indicated and pressed together in the directions indicated by the two block arrows, wherein each of the plurality of discrete second electrodes (e.g., second electrode 230) is covered by the folded portion of separator 250. A battery including a folded electrochemical device (e.g., a folded multi-cell structure as shown in fig. 6A) may be easier and faster to produce than a battery having a stacked configuration. Such embodiments of electrochemical devices including a discrete second electrode may be electrically connected (e.g., to an external load) via a discrete second current collector (e.g., second current collector 225 in fig. 6A) and a current collector bus of an article (e.g., article 100).

Although a plurality of discrete second electrodes are described as being associated with the discrete second current collectors above, the electrochemical device may include a continuous second current collector segment adjacent the plurality of discrete second electrodes. Such embodiments may allow for even easier fabrication (e.g., by jumping the electrode active material of the second electrode onto a continuous electronically conductive layer).

In some embodiments, the electrochemical device comprises a continuous second electrode. For example, fig. 6B illustrates a non-limiting embodiment of an electrochemical device 200, the electrochemical device 200 including a continuous second electrode 230 (electronically coupled to a second current collector 225) separated from the article 100 by a continuous separator 250. As in the case of the discrete second electrode described above, in certain embodiments, the embodiment of the electrochemical device 200 shown in fig. 6B may be folded. For example, referring to fig. 6B, according to certain embodiments, the article 100, the separator 250 (e.g., a continuous separator), the second electrode 230, and the continuous second current collector 225 are folded as indicated and pressed together in the directions indicated by the two block arrows, wherein each of the folded portions of the second electrode 230 effectively forms a double-sided electrode covered by the folded portion of the separator 250. Electrical connections (e.g., to an external circuit) may be made, for example, at the folds of the continuous second current collector.

A useful feature of some such folded electrochemical devices, which include a plurality of discrete second electrodes and/or a continuous second electrode electronically coupled to a continuous second current collector, is that, in some such cases, there is a continuous electronically conductive path available for the second electrode. Thus, if the electrical connection between the second current collector and the external circuit is broken (e.g., due to a manufacturing failure or due to damage to the electrochemical device), the current generated in the region proximate the broken electrical connection at the second electrode may flow along the second current collector until the current reaches an uninterrupted electrical connection.

In some cases, at least one of the discrete electrode segments in the electrochemical device loses electronic coupling with the current collector bus (e.g., due, at least in part, to a change in volume of the substrate of the article in the electrochemical device). In some cases, due to the articles having the configurations described herein, the electrochemical device may still be charged and/or discharged after a loss of electronic coupling between at least one of the electrode segments and the current collector bus. Referring to fig. 6B, in some cases, the discrete electrode segments 130a lose electronic coupling with the current collector bus (not shown) (e.g., due to thermally induced volumetric changes of the substrate 120). However, according to certain embodiments, the electrochemical device 200 in fig. 6B may still be charged/discharged even after a loss of coupling of the discrete electrode segments 130a and the current collector bus. This is because the loss of coupling between the discrete electrode segments 130a and the collector bus electrically isolates the discrete electrode segments 130a from the rest of the electrochemical device 200 (preventing problems such as thermal runaway), while at least some of the remaining discrete electrode segments remain electronically coupled to the collector bus, allowing the electrochemical device 200 to be charged/discharged.

As mentioned above, in some embodiments, the substrate of an article or electrochemical device described herein is or includes a release layer. The release layers described herein are constructed and arranged to have one or more of the following characteristics: relatively good adhesion to a first layer (e.g., a current collector domain, a plurality of discrete electrode segments, or, in other embodiments, another layer of the substrate or other layer), but relatively moderate or poor adhesion to a second layer (e.g., from a structure used to make the article); high mechanical stability for promoting delamination without mechanical disintegration; high thermal stability; and compatibility with processing conditions (e.g., deposition of layers on top of the release layer, and compatibility with the techniques used to form the release layer). If the release layer is incorporated into an electrochemical device (e.g., an electrochemical cell), the release layer can be thin (e.g., less than about 10 microns) to reduce the total cell weight. The release layer should also be smooth and uniform in thickness to facilitate the formation of a uniform layer on top of the release layer. Furthermore, the release layer should be stable in the electrolyte and should not interfere with the structural integrity of the electrodes so that the electrochemical cell has a high electrochemical "capacity" or energy storage capability (i.e., reduced capacity fade). The use of a Release layer to remove objects from one or more components of an Electrochemical device is described in detail in U.S. patent application serial No. 12/862,513 entitled "Release System for Electrochemical Cells," filed 24.8.2010.

The substrate and/or release layer may be formed of, for example, a ceramic, a polymer, or a combination thereof. Thus, the substrate and/or the exfoliation layer may be semiconducting or insulating. In some embodiments, the substrate and/or release layer comprises a polymeric material. In some cases, at least a portion of the polymeric material of the substrate and/or release layer is crosslinked; in other cases, the polymeric material is substantially uncrosslinked. Examples of polymeric materials include, for example, hydroxyl-containing polymers such as polyvinyl alcohol, polyvinyl butyral, polyvinyl formal, vinyl acetate-vinyl alcohol copolymer, ethylene-vinyl alcohol copolymer, and vinyl alcohol-methyl methacrylate copolymer. As noted above, in some, but not necessarily all, embodiments, the substrate (e.g., including the release layer) comprises a heat-shrinkable film.

The electrode described herein (e.g., a plurality of discrete electrode segments, a second electrode of an electrochemical device) can be an anode comprising a plurality of anode active materials. For example, the anode may include a lithium-containing material, where lithium is the anode active material. Suitable electroactive materials for use as anode active materials in the anodes described herein include, but are not limited to, lithium metals such as lithium foil and lithium deposited on a conductive substrate, and lithium alloys (e.g., lithium aluminum alloys and lithium tin alloys). Methods for depositing negative electrode materials (e.g., alkali metal anodes such as lithium) onto a substrate may include methods such as thermal evaporation, sputtering, jet vapor deposition, and laser ablation. Alternatively, where the anode comprises a lithium foil or a lithium foil and a substrate, these may be laminated together by lamination processes known in the art to form the anode.

In some embodiments, the anode is an electrode from which lithium ions are released during discharge and into which lithium ions are integrated (e.g., intercalated) during charging. In some embodiments, the anode active material is a lithium intercalation compound (e.g., a compound capable of reversibly intercalating lithium ions at lattice sites and/or interstitial sites). In some embodiments, the anode active material comprises carbon. In some cases, the anode active material is or includes a graphitic material (e.g., graphite). Graphitic materials generally refer to materials comprising multiple graphene layers (i.e., layers comprising carbon atoms covalently bonded in a hexagonal lattice). Adjacent graphene layers are typically attracted to each other via van der waals forces, although in some cases covalent bonds may exist between one or more sheets. In some cases, the carbonaceous anode active material is or includes coke (e.g., petroleum coke). In certain embodiments, the anode active material comprises any alloy of silicon, lithium, and/or combinations thereof. In certain embodiments, the anode active material comprises lithium titanate (Li) ₄Ti₅O₁₂Also known as "LTO"), tin-cobalt oxide, or any combination thereof.

In one embodiment, the electroactive lithium-containing material of the anode comprises greater than 50% by weight lithium. In another embodiment, the electroactive lithium-containing material of the anode comprises greater than 75% by weight lithium. In yet another embodiment, the electroactive lithium-containing material of the anode comprises greater than 90% by weight lithium. Additional materials and arrangements suitable for use in anodes are described, for example, in U.S. patent publication No. 2010/0035128 entitled "Application of Force in Electrochemical Cells" filed on 8/4 of 2009 by Scordilis-Kelley et al, which is incorporated herein by reference in its entirety for all purposes.

The electrode described herein (e.g., a plurality of discrete electrode segments, a second electrode of an electrochemical device) can be a cathode that includes a cathode active material. Suitable electroactive materials for use as cathode active materials in the cathode include, but are not limited to, one or more metal oxides, one or more intercalation materials, electroactive transition metal chalcogenides, electroactive conductive polymers, sulfur, carbon, and/or combinations thereof.

In some embodiments, the cathode active material includes one or more metal oxides. In some embodiments, an intercalation cathode (e.g., a lithium intercalation cathode) can be used. Non-limiting examples of suitable materials that can embed ions of the electroactive material (e.g., alkali metal ions) include metal oxides, titanium sulfide, and iron sulfide. In some embodiments, the cathode is an intercalation cathode that includes a lithium transition metal oxide or lithium transition metal phosphate. Further examples include Li _xCoO₂(for example, Li)_1.1CoO₂)、Li_xNiO₂、Li_xMnO₂、Li_xMn₂O₄(for example, Li)_1.05Mn₂O₄)、Li_xCoPO₄、Li_xMnPO₄、LiCo_xNi_(1-x)O₂And LiCo_xNi_yMn_(1-x-y)O₂(e.g., LiNi)_1/3Mn_1/3Co_1/3O₂、LiNi_3/5Mn_1/5Co_1/5O₂、LiNi_4/ ₅Mn_1/10Co_1/10O₂、LiNi_1/2Mn_3/10Co_1/5O₂). X may be greater than or equal to 0 and less than or equal to 2. X is typically greater than or equal to 1 and less than or equal to 2 when the electrochemical device is fully discharged, and X is typically less than 1 when the electrochemical device is fully charged. In some embodiments, a fully charged electrochemical device can have an x value greater than or equal to 1 and less than or equal to 1.05, greater than or equal to 1 and less than or equal to 1.1, or greater than or equal to 1 and less than or equal to 1.2. Other examples include: li_xNiPO₄Wherein (0)<x≤1)；LiMn_xNi_yO₄Wherein (x + y ═ 2) (e.g., LiMn_1.5Ni_0.5O₄)；LiNi_xCo_yAl_zO₂Wherein (x + y + z ═ 1); LiFePO₄(ii) a And combinations thereof. In some embodiments, the electroactive material within the cathode includes a lithium transition metal phosphate (e.g., LiFePO)₄) The lithium transition metal phosphate may be substituted with borates and/or silicates in certain embodiments.

As described above, in some embodiments, the cathode active material includes one or more chalcogenides. As used herein, the term "chalcogenide" relates to a compound of one or more of the elements comprising oxygen, sulfur and selenium. Examples of suitable transition metal chalcogenides include, but are not limited to, electroactive oxides, sulfides, and selenides of transition metals selected from the group consisting of Mn, V, Cr, Ti, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, and Ir. In one embodiment, the transition metal chalcogenide is selected from the group consisting of electroactive oxides of nickel, manganese, cobalt, and vanadium, and electroactive sulfides of iron. In one embodiment, the cathode comprises one or more of the following materials: manganese dioxide, iodine, silver chromate, silver oxide and vanadium pentoxide, copper oxide, copper oxyphosphate, lead sulfide, copper sulfide, iron sulfide, lead bismuthate, bismuth trioxide, cobalt dioxide, copper chloride, manganese dioxide and carbon. In another embodiment, the cathode active layer comprises an electroactive conductive polymer. Examples of suitable electroactive conductive polymers include, but are not limited to, electroactive and electronically conductive polymers selected from the group consisting of polypyrrole, polyaniline, polyphenylene, polythiophene, and polyacetylene. Examples of the conductive polymer include polypyrrole, polyaniline, and polyacetylene.

In some embodiments, electroactive materials for use as cathode active materials in the cathodes described herein include electroactive sulfur-containing materials. As used herein, "electroactive sulfur-containing material" is associated with a cathode active material that includes elemental sulfur in any form, where electrochemical activity involves the oxidation or reduction of a sulfur atom or sulfur moiety. As is known in the art, the properties of electroactive sulfur-containing materials useful in the practice of the invention can vary widely. For example, in one embodiment, the electroactive sulfur-containing material comprises elemental sulfur. In another embodiment, the electroactive sulfur-containing material comprises a mixture of elemental sulfur and a sulfur-containing polymer. Thus, suitable electroactive sulfur-containing materials can include, but are not limited to, elemental sulfur, as well as organic materials that include sulfur atoms and carbon atoms, which may or may not be polymeric. Suitable organic materials include those that also include heteroatoms, conductive polymer segments, composites, and conductive polymers.

In some embodiments, the electroactive sulfur-containing material of the cathode active material comprises greater than 50 wt% sulfur. In another embodiment, the electroactive sulfur-containing material comprises greater than 75% by weight of sulfur. In yet another embodiment, the electroactive sulfur-containing material comprises greater than 90% by weight of sulfur.

The cathode of the present invention can include from about 20 wt% to 100 wt% of an electroactive cathode material (e.g., as measured after an appropriate amount of solvent has been removed from the cathode active layer and/or after the layer has been suitably cured). In one embodiment, the amount of electroactive sulfur-containing material in the cathode is in a range of 5 wt% to 30 wt% of the cathode. In another embodiment, the amount of electroactive sulfur-containing material in the cathode is in a range of 20 wt.% to 90 wt.% of the cathode.

Additional materials suitable for use in Cathodes and suitable methods for making Cathodes are described in, for example, U.S. patent publication No. 5,919,587 entitled "Novel Composite Cathodes, Electrochemical Cells composing Novel composites Cathodes, and Processes for manufacturing Same," filed on 5/21 1997 and U.S. patent publication No. 2010/0035128 entitled "Application of Force in Electrochemical Cells," filed on 8/4 2009 to Scordiis-Kelley et al, each of which is incorporated herein by reference in its entirety for all purposes.

In some embodiments, the electrodes (e.g., discrete electrode segments, anode portions) of an electrochemical device may include one or more coatings or layers formed from polymers, ceramics, and/or glasses. The coating may serve as a protective layer and may serve different functions. These functions may include: prevent dendrite formation during recharging, which could otherwise lead to short circuits; preventing reaction of the electrode active material with the electrolyte; and improved cycle life. Examples of such protective layers include those described in: U.S. patent No. 8,338,034 to Affinito et al and U.S. patent publication No. 2015/0236322 to larami et al, each of which is incorporated herein by reference in its entirety for all purposes.

The electrochemical devices described herein may include an electrolyte. The electrolyte may act as a medium for the storage and transport of ions, and in the particular case of solid and gel electrolytes, these materials may additionally act as a separator between the anode and the cathode. Any liquid, solid, or gel material capable of storing and transporting ions may be used, so long as the material facilitates the transport of ions (e.g., lithium ions) between the anode and cathode. The electrolyte is non-electronically conductive to prevent shorting between the anode and cathode. In some embodiments, the electrolyte may comprise a non-solid electrolyte.

In some embodiments, the electrolyte comprises a fluid that may be added at any point in the manufacturing process. In some cases, an electrochemical device can be fabricated by providing a cathode and an anode, applying a component anisotropic force perpendicular to the active surface of the anode, and then adding a fluid electrolyte such that the electrolyte is in electrochemical communication with the cathode and the anode. In other cases, a fluid electrolyte may be added to the electrochemical device prior to or simultaneously with the application of the anisotropic force component, after which the electrolyte is in electrochemical communication with the cathode and anode.

The electrolyte may include one or more ionic electrolyte salts for providing ionic conductivity and one or more liquid electrolyte solvents, gel polymer materials, or polymer materials. Suitable non-aqueous electrolytes may include organic electrolytes comprising one or more materials selected from the group consisting of liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes. Examples of nonaqueous electrolytes for Lithium Batteries are described by Dorniney in Lithium Batteries, New Materials, Developments and Perspectives, Chapter 4, pp.137-165, Elsevier, Amsterdam (1994). Examples of gel polymer electrolytes and solid polymer electrolytes are described by Alamgil et al in Lithium Batteries, New Materials, Developments and Perspectives, Chapter 3, pp.93-136, Elsevier, Amsterdam (1994). Heterogeneous electrolyte compositions that may be used in the batteries described herein are described by Mikhaylik et al, U.S. patent application serial No. 12/312,764 entitled "Separation of Electrolytes" filed on 26.5.2009, which is incorporated herein by reference in its entirety.

Examples of useful non-aqueous liquid electrolyte solvents include, but are not limited to, non-aqueous organic solvents such as, for example, N-methylacetamide, acetonitrile, acetals, ketals, esters, carbonates, sulfones, sulfites, sulfolanes, aliphatic ethers, cyclic ethers, glymes, polyethers, phosphate esters, siloxanes, dioxolanes, N-alkylpyrrolidones, substituted versions of the foregoing, and blends thereof. The aforementioned fluorinated derivatives may also be used as liquid electrolyte solvents.

In some cases, for example, in lithium batteries, an aqueous solvent may be used as the electrolyte. The aqueous solvent may comprise water, which may comprise other components, such as ionic salts. As described above, in some embodiments, the electrolyte may include a substance such as lithium hydroxide, or other substance that makes the electrolyte alkaline, to reduce the concentration of hydrogen ions in the electrolyte.

The liquid electrolyte solvent may also serve as a plasticizer for the gel polymer electrolyte (i.e., an electrolyte comprising one or more polymers that form a semi-solid network structure). Examples of useful gel polymer electrolytes include, but are not limited to, those comprising one or more polymers selected from the group consisting of: polyethylene oxide, polypropylene oxide, polyacrylonitrile, polysiloxane, polyimide, polyphosphazene, polyether, sulfonated polyimide, perfluorinated membranes (NAFION resin), polydivinyl polyethylene glycol, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polysulfone, polyethersulfone, derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing, and optionally one or more plasticizers. In some embodiments, the gel polymer electrolyte comprises between 10% and 20%, between 20% and 40%, between 60% and 70%, between 70% and 80%, between 80% and 90%, or between 90% and 95% heterogeneous electrolyte by volume.

In some embodiments, one or more solid polymers may be used to form the electrolyte. Examples of useful solid polymer electrolytes include, but are not limited to, those comprising one or more polymers selected from the group consisting of: polyethers, polyethylene oxides, polypropylene oxides, polyimides, polyphosphazenes, polyacrylonitriles, polysiloxanes, derivatives of the foregoing, copolymers of the foregoing, crosslinked and network structures of the foregoing, and blends of the foregoing.

In addition to electrolyte solvents, gelling agents, and polymers known in the art for forming electrolytes, the electrolytes may also include one or more ionic electrolyte salts also known in the art to enhance ionic conductivity.

Examples of ionic electrolyte salts for use in the electrolyte of the electrochemical devices (e.g., electrochemical cells) described herein include, but are not limited to: LiSCN, LiBr, LiI, LiClO₄、LiAsF₆、LiSO₃CF₃、LiSO₃CH₃、LiBF₄、LiB(Ph)₄、LiPF₆、LiC(SO₂CF₃)₃、LiN(SO₂CF₃)₂And lithium bis (fluorosulfonyl) imide (LiFSI). Other electrolyte salts that may be useful include lithium polysulfides (Li)₂S_x) And lithium salts of organic polysulfides (LiS)_xR)_nWherein x is an integer from 1 to 20, n is an integer from 1 to 3, and R is an organic group; and those disclosed in U.S. patent No. 5,538,812 to Lee et al, which is incorporated herein by reference in its entirety for all purposes.

In some embodiments, the electrolyte comprises one or more room temperature ionic liquids. Room temperature ionic liquid (if present) solventOften comprising one or more cations and one or more anions. Non-limiting examples of suitable cations include lithium cations and/or one or more quaternary ammonium cations, such as imidazole cations, pyrrolidine cations, pyridine cations, tetraalkylammonium cations, pyrazole cations, piperidine cations, pyridazine cations, pyrimidine cations, pyrazine cations, oxazole cations, and triazole cations. Non-limiting examples of suitable anions include trifluoromethylsulfonate (CF)₃SO₃ ^-) Bis (fluorosulfonyl) imide (N (FSO)₂)₂ ^-) Bis (trifluoromethylsulfonyl) imide ((CF)₃SO₂)₂N^-) Bis (perfluoroethylsulfonyl) imide ((CF)₃CF₂SO₂)₂N^-) And tris (trifluoromethylsulfonyl) methide ((CF)₃SO₂)₃C^-). Non-limiting examples of suitable ionic liquids include N-methyl-N-propylpyrrolidine/bis (fluorosulfonyl) imide and 1, 2-dimethyl-3-propylimidazole/bis (trifluoromethanesulfonyl) imide. In some embodiments, the electrolyte comprises both a room temperature ionic liquid and a lithium salt. In other embodiments, the electrolyte comprises a room temperature ionic liquid and does not comprise a lithium salt.

In some embodiments described herein, one or more forces are applied to a portion of an electrochemical device. Such application of force may reduce irregularities or roughening of the electrode surface of the cell (e.g., when a lithium metal or lithium alloy anode is employed), thereby improving performance. Electrochemical devices in which anisotropic forces are applied and methods for applying such forces are described, for example, in U.S. patent No. 9,105,938 issued on 11/8/11/2010 as U.S. patent publication No. 2010/0035128 entitled "Application of Force in Electrochemical Cells," which is incorporated herein by reference in its entirety for all purposes.

In some cases, the force may include an anisotropic force having a component perpendicular to an active surface of an anode of the electrochemical device. In embodiments described herein, an electrochemical device (e.g., a rechargeable battery) can be subjected to charge/discharge cycles involving deposition of a metal (e.g., lithium metal or other active material) on the surface of the anode upon charging and reaction of the metal on the surface of the anode upon discharging, wherein the metal diffuses from the anode surface. The uniformity of metal deposition on the anode can affect cell performance. For example, when lithium metal is removed from and/or redeposited on the anode, it may create an uneven surface in some cases. For example, upon redeposition, it may deposit unevenly, forming a rough surface. Roughened surfaces can increase the amount of lithium metal available for undesirable chemical reactions, which can lead to reduced cycle life and/or poor battery performance. In accordance with certain embodiments described herein, it has been found that applying a force to an electrochemical device reduces such behavior and improves the cycle life and/or performance of the battery.

In some embodiments, the electrochemical device is constructed and arranged to apply an anisotropic force having a component perpendicular to the first anode active surface portion for at least one period of time during charging and/or discharging of the device. Referring back to fig. 9B, which illustrates an exemplary folded electrochemical device as described herein, a force may be applied in the direction of arrow 481. The arrow 482 shows the component of the force 481 perpendicular to the first anode active surface portion 441 of the first anode portion 431 and to the first cathode active surface portion 541 of the first cathode portion 531.

In some embodiments, the anisotropic force having a component perpendicular to the active surface of the anode is applied for at least one time period during charging and/or discharging of the electrochemical device. In some embodiments, the force may be applied continuously over a period of time or over multiple periods of time that may vary in duration and/or frequency. In some cases, the anisotropic force may be applied at one or more predetermined locations, optionally distributed on the active surface of the anode. In some embodiments, the anisotropic force is applied uniformly on one or more active surfaces of the anode.

"anisotropic force" is given its ordinary meaning in the art and means a force that is not equal in all directions. A force that is equal in all directions is, for example, the internal pressure of the fluid or material within the fluid or material, such as the internal air pressure of the object. Examples of forces that are unequal in all directions include forces that are directed in a particular direction, such as a force exerted by an object on a table through gravity on the table. Another example of an anisotropic force includes certain forces exerted by a band disposed around the perimeter of the object. For example, a bungee cord or turnbuckle may apply a force around the perimeter of the object it wraps around. However, the belt does not exert any direct force on any portion of the outer surface of the object that is not in contact with the belt. Further, when the belt stretches along the first axis to a greater extent than the second axis, the belt may exert a greater force in a direction parallel to the first axis than a force exerted parallel to the second axis.

A force having a "perpendicular component" to a surface (e.g., the active surface of the anode) is given its ordinary meaning as would be understood by one of ordinary skill in the art and includes, for example, a force that acts at least partially in a direction substantially perpendicular to the surface. Other examples of such terms, particularly terms applied in the description of this document, will be understood by the skilled person.

In some embodiments, the anisotropic force may be applied such that the magnitude of the force is substantially equal in all directions within a plane defining a cross-section of the electrochemical device, but the magnitude of the force in the out-of-plane direction is not substantially equal to the magnitude of the in-plane force.

In one set of embodiments, the battery described herein is constructed and arranged to apply an anisotropic force having a component perpendicular to the active surface of the anode for at least one period of time during charging and/or discharging of the battery. The meaning will be understood by those of ordinary skill in the art. In such an arrangement, the battery may be formed as part of a container that applies such force by virtue of a "load" applied during or after assembly of the battery or during use of the battery due to expansion and/or contraction of one or more portions of the battery itself.

In some embodiments, the magnitude of the applied force is large enough to enhance the performance of the electrochemical device. In some cases, the anode active surface and the anisotropic force may be simultaneously selected such that the anisotropic force affects the surface topography of the anode active surface to inhibit increase of the anode active surface area by charging and discharging, and wherein the anode active surface area is increased to a greater extent by charging and discharging cycles under conditions that are free of the anisotropic force but otherwise substantially the same. In this context, "substantially the same conditions" means similar or identical conditions except for the application and/or magnitude of the force. For example, otherwise the same conditions may mean the same cell, but where it is not configured to apply an anisotropic force (e.g., through a bracket or other connection) to the cell under test.

In some embodiments, the anisotropic force having a component perpendicular to the active surface of the anode is applied to the following extent during at least one time period during charging and/or discharging of the electrochemical device: the anisotropic force effectively suppresses an increase in the surface area of the anode active surface relative to an increase in the surface area without the anisotropic force. The component of the anisotropic force perpendicular to the active surface of the anode can, for example, define a pressure of at least about 4.9 newtons per square centimeter, at least about 9.8 newtons per square centimeter, at least about 24.5 newtons per square centimeter, at least about 49 newtons per square centimeter, at least about 78 newtons per square centimeter, at least about 98 newtons per square centimeter, at least about 117.6 newtons per square centimeter, at least about 147 newtons per square centimeter, at least about 175 newtons per square centimeter, at least about 200 newtons per square centimeter, at least about 225 newtons per square centimeter, or at least about 250 newtons per square centimeter. In some embodiments, the component of the anisotropic force normal to the active surface of the anode can be defined, for example, as less than about 250 newtons per square centimeter, less than about 225 newtons per square centimeter, less than about 196 newtons per square centimeter, less than about 147 newtons per square centimeter, less than about 117.6 newtons per square centimeter, less than about 98 newtons per square centimeter, less than about 49 newtons per square centimeter, less than about 24.5 newtons per square centimeter A square centimeter, or a pressure less than about 9.8 newtons per square centimeter. In some cases, the component of the anisotropic force perpendicular to the active surface of the anode can define a pressure between about 4.9 newtons per square centimeter and about 147 newtons per square centimeter, between about 49 newtons per square centimeter and about 117.6 newtons per square centimeter, between about 68.6 newtons per square centimeter and about 98 newtons per square centimeter, between about 78 newtons per square centimeter and about 108 newtons per square centimeter, between about 4.9 newtons per square centimeter and about 250 newtons per square centimeter, between about 49 newtons per square centimeter and about 250 newtons per square centimeter, between about 80 newtons per square centimeter and about 250 newtons per square centimeter, between about 90 newtons per square centimeter and about 250 newtons per square centimeter, or between about 100 newtons per square centimeter and about 250 newtons per square centimeter. In some embodiments, the force or pressure may be applied externally to the cell, as described herein. Although the force and pressure are generally described herein in units of newtons and newtons per unit area, respectively, the force and pressure may also be in units of kilogram-force (kg), respectively_f) And kilogram force per unit area. One of ordinary skill in the art will be familiar with units based on kilogram force, and will understand that 1 kilogram force is equal to about 9.8 newtons.

As described herein, in some embodiments, the surface of the anode may be enhanced during cycling by applying externally applied (in some embodiments, uniaxial) pressure (e.g., for lithium, the development of moss-like or rough surfaces of lithium may be reduced or eliminated). In some embodiments, the externally applied pressure may be selected to be greater than the yield stress of the material forming the anode. For example, for anodes comprising lithium, the cell may have an anisotropic force under an externally applied anisotropic force having a defined value of at least about 8kg_f/cm²At least about 9kg_f/cm²At least about 10kg_f/cm²At least about 20kg_f/cm²At least about 30kg_f/cm²At least about 40kg_f/cm²Or at least about 50kg_f/cm²Of the pressure of. This is because the yield stress of lithium is about 7kg_f/cm²To 8kg_f/cm². Thus, at pressures greater than this value (e.g., uniaxial pressures), moss Li or any surface roughness can be reduced or inhibited. The lithium surface roughness may mimic a surface pressed thereon. Therefore, when the amount is at least about 8kg_f/cm²At least about 9kg_f/cm²Or at least about 10kg_f/cm²At least about 20kg_f/cm²At least about 30kg_f/cm²At least about 40kg_f/cm²Or at least about 50kg_f/cm²When the pressing surface is smooth, the lithium surface may become smoother with the cycle when the pressure applied from the outside is cycled. As described herein, the pressing surface may be varied by selecting a suitable material between the anode and cathode.

In some cases, one or more forces applied to the cell have a component that is non-perpendicular to the active surface of the anode. For example, in fig. 9B, the force 484 is not perpendicular to the first anode active surface portion 441. In one set of embodiments, the sum of the components of all applied anisotropic forces in a direction perpendicular to the anode active surface is greater than the sum of any components in a direction non-perpendicular to the anode active surface. In some embodiments, the sum of the components of all applied anisotropic forces in a direction perpendicular to the anode active surface is at least about 5%, at least about 10%, at least about 20%, at least about 35%, at least about 50%, at least about 75%, at least about 90%, at least about 95%, at least about 99%, or at least about 99.9% greater than the sum of any components in a direction parallel to the anode active surface.

Any suitable method known in the art may be used to apply the anisotropic forces described herein. In some embodiments, the force may be applied using a compression spring. For example, the electrochemical device can be located in an optional closed container structure having one or more compression springs located between the current collector and/or the current collector and an adjacent wall of the container structure to generate a force having a component perpendicular to the anode active surface (e.g., an anode active surface portion). In some embodiments, the force may be applied by placing one or more compression springs outside of the container structure such that the springs are located between an outside surface of the container structure and another surface (e.g., a table top, an inside surface of another container structure, an adjacent battery, etc.). Another element (inside or outside the containment structure) may be used to apply the force, including but not limited to Belleville washers, machine screws, pneumatics, and/or weights, etc. For example, in one set of embodiments, one or more batteries (e.g., a folded multi-cell system as described herein) are disposed between two plates (e.g., metal plates). Means (e.g., mechanical screws, springs, etc.) may be used to apply pressure through the plates to the ends of the cells or stacks. For example, in the case of a mechanical screw, the cell may be compressed between the plates as the screw is rotated. As another example, in some embodiments, one or more wedges may be disposed between a surface of a battery (or a container structure surrounding a battery) and a fixed surface (e.g., a table top, an inside surface of another container structure, an adjacent battery, etc.). The anisotropic force may be applied by applying a force on the wedge (e.g., by turning a mechanical screw) to drive the wedge between the battery and the adjacent fixed surface.

In some cases, the electrochemical devices may be pre-compressed prior to insertion into the containment structure, and when inserted into the containment structure, they may expand to produce a net force on the cell. Such an arrangement may be advantageous, for example, if the battery is capable of withstanding relatively high pressure variations. In such embodiments, the container structure may have a relatively high strength (e.g., at least about 100MPa, at least about 200MPa, at least about 500MPa, or at least about 1 GPa). Further, the container structure may have a relatively high modulus of elasticity (e.g., at least about 10GPa, at least about 25GPa, at least about 50GPa, or at least about 100 GPa). The container structure may comprise, for example, aluminum, titanium, or any other suitable material.

In some embodiments, the use of certain electrically insulating regions and/or methods described herein may result in improved capacity after repeated cycling of the electrochemical device. For example, in some embodiments, after alternately discharging and charging the battery three times, the battery exhibits at least about 50%, at least about 80%, at least about 90%, or at least about 95% of the initial capacity of the battery at the end of the third cycle. In some cases, after alternately discharging and charging the battery ten times, the battery exhibits at least about 50%, at least about 80%, at least about 90%, or at least about 95% of the initial capacity of the battery at the end of the tenth cycle. In yet another instance, after alternately discharging and charging the battery twenty-five times, the battery exhibits at least about 50%, at least about 80%, at least about 90%, or at least about 95% of the initial capacity of the battery at the end of the twenty-fifth cycle. In some embodiments, the electrochemical device has a capacity of at least 20mAh, 30mAh, 40mAh, 50mAh, 60mAh, 70mAh, or 80mAh at the end of the third, tenth, twenty-fifth, thirty-fifth, forty-fifth, fifty-fifth, or sixty cycles of the battery.

It will be understood that when a portion (e.g., a layer, structure, region) is "on," "adjacent to," above, "on," "over," or "supported by" another portion, it can be directly on the portion, or intervening portions (e.g., layers, structures, regions) may also be present. Similarly, when a portion is "under" or "beneath" another portion, it can be directly under the portion, or intervening portions (e.g., layers, structures, regions) can also be present. A portion that is "directly on," "directly adjacent to," "immediately adjacent to," "directly in contact with," or "directly supported by" another portion means that there is no intervening portion present. It will also be understood that when a portion is referred to as being "on," above, "adjacent," over, "" covering, "in" contact, "under" or "supported" by another portion, it can cover the entire portion or a portion of the portion.

As noted above, certain embodiments of the systems and/or methods of the present invention include one or more processors, e.g., associated with a sensor. According to some embodiments, the processor may be part of a computer-implemented control system. A computer-implemented control system may be used to operate various components of the system. In general, any of the computing methods, steps, simulations, algorithms, systems, and system elements described herein may be implemented and/or controlled using one or more computer-implemented control systems, such as the various embodiments of computer-implemented systems described below. The implementation of the methods, steps, control systems, and control system elements described herein is not limited to any particular computer system described herein, as many other different machines may be used.

The computer-implemented control system may be part of or operatively associated with one or more articles of manufacture (e.g., electrochemical cells) and/or other system components, and in some embodiments is configured and/or programmed to control and adjust operating parameters, as well as analyze and calculate values, such as any of the values described above. In some embodiments, a computer-implemented control system may send and receive reference signals to set and/or control operating parameters of system devices. In other embodiments, the computer-implemented system may be separate from and/or remotely located relative to other system components, and may be configured to receive data from one or more of the present systems via indirect and/or portable means, e.g., via a portable electronic data storage device such as a diskette, or via communication over a computer network (e.g., the internet or a local intranet).

The computer-implemented control system may include several known components and circuitry, including a processor, a memory system, input and output devices and interfaces (e.g., interconnection mechanisms), and other components, such as transmission circuitry (e.g., one or more buses), video and audio data input/output (I/O) subsystems, dedicated hardware, and other components and circuitry, as described in more detail below. Further, the computer system may be a multi-processor computer system, or may include multiple computers connected by a computer network.

The computer-implemented control system may include a processor, such as a commercially available processor, for example, one of the series x86, Celeron, Pentium, and Core processors available from Intel; similar devices from AMD and Cyrix; a 680X0 series microprocessor available from Motorola and a PowerPC microprocessor from IBM. Many other processors are available, and the computer system is not limited to a particular processor.

Processors typically execute programs referred to as operating systems, examples of which are Windows NT, Windows 95 or Windows 98, Windows XP, Windows Vista, Windows7, Windows 10, UNIX, Linux, DOS, VMS, MacOS, OS8, and OSX, which control the execution of other computer programs, and provide scheduling, debugging, input/output control, computing, compiling, memory allocation, data management and memory management, communication control, and related services. According to some embodiments, the processor and operating system together define a computer platform on which application programs in a high-level programming language are written. The computer-implemented control system is not limited to a particular computer platform.

According to some embodiments, the processor typically operates on data within the integrated circuit memory elements according to program instructions and then copies the operated-on data to the non-volatile recording medium after processing is completed. Various mechanisms for managing data movement between a nonvolatile recording medium and an integrated circuit memory element are known, and a computer-implemented control system implementing the above-described method, steps, system control, and system element control is not limited thereto. The computer-implemented control system is not limited to a particular memory system.

At least a portion of such memory systems described above may be used to store one or more data structures (e.g., look-up tables) or equations such as calibration curve equations. For example, at least a portion of the non-volatile recording medium may store at least a portion of a database that includes one or more such data structures. Such a database may be any of various types of databases, such as: a file system comprising one or more flat file data structures, wherein data is organized into data units separated by delimiters; a relational database in which data is organized into data units stored in tables; an object-oriented database in which data is organized into data units stored as objects; other types of databases, or any combination thereof.

It should be appreciated that one or more of any type of computer-implemented control system may be used to implement the various embodiments described herein. Aspects of the invention may be implemented in software, hardware or firmware, or any combination thereof. The computer-implemented control system may include specially-programmed, special-purpose hardware, such as an application-specific integrated circuit (ASIC). Such dedicated hardware may be configured to implement one or more of the above-described methods, steps, algorithms, system controls, and/or system element controls as part of the above-described computer-implemented control system or as a stand-alone component.

The computer-implemented control system and its components can be programmed using any of a variety of one or more suitable computer programming languages. Additionally, the methods, steps, algorithms, system controls, and/or system element controls may be implemented using any of a variety of suitable programming languages. Such languages may include: process programming languages such as Lab View, C, Pascal, Fortran, and BASIC; object-oriented languages such as C + +, Java, and Eiffel; and other languages such as scripting languages or even assembly languages. In some embodiments, the computer programming language is Python. In some embodiments, the computer programming language is SQL.

Such methods, steps, algorithms, system control, and/or system element control may be implemented, alone or in combination, as a computer program product tangibly embodied as a computer-readable signal on a computer-readable medium, e.g., a non-volatile recording medium, an integrated circuit memory element, or a combination thereof. For each such method, step, simulation, algorithm, system control, or system element control, such a computer program product may comprise a computer-readable signal tangibly embodied on a computer-readable medium, defining instructions, for example, as part of one or more programs that, as a result of being executed by a computer, instruct the computer to perform the method, step, algorithm, system control, and/or system element control.

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U.S. patent publication No. US 2013/0095380, published on 18/4/2013, filed on 4/2012 as application No. 13/644,933, on 20/1/2015 as U.S. patent No. 8.936,870, entitled "Electrode Structure and Method for Making the Same; U.S. patent publication No. US 2014/0123477, filed as application No. 14/069,698 on 1/11 in 2013, patented as U.S. patent No. 9,005,311 on 14/4/2015 and published on 8/5/2014 entitled "Electrode Active Surface Pretreatment"; U.S. patent publication No. US2014/0193723, filed as application No. 14/150,156 on 8/1/2014 and patented as U.S. patent No. 9,559,348 on 31/1/31/2017 and published on 10/7/2014 entitled "reduction Control in Electrochemical Cells"; U.S. patent publication No. US 2014/0255780, filed as application No. 14/197,782 on 5/3 in 2014, patented as U.S. patent No. 9,490,478 on 6/11/2016 and published on 11/9/2014 entitled "Electrochemical Cells compounding fibre Materials"; U.S. patent publication No. US 2014/0272594, filed on 15.3.2013 as application No. 13/833,377 and published on 18.9.2014 entitled "Protective Structures for Electrodes"; U.S. patent publication No. US 2014/0272597, filed as application No. 14/209,274 on 13/3/2014 and published 18/9/2014 entitled "Protected Electrode Structures and Methods"; U.S. patent publication No. US 2014/0193713, filed as application No. 14/150,196 on 8/1 in 2014, patented as U.S. patent No. 9,531,009 on 27/12/2016 and published on 10/7/2014 entitled "licensing of Electrodes in Electrochemical Cells"; U.S. patent publication No. US 2014/0272565, filed as application No. 14/209,396 on 3/13 of 2014 and published on 18/9 of 2014 entitled "Protected Electrode Structures"; U.S. patent publication No. US 2015/0010804, published on 8/1/2015, filed on 3/7/2014 as application No. 14/323,269 and entitled "Ceramic/Polymer Matrix for Electrode Protection in Electrochemical Cells, incorporated Rechargeable Lithium Batteries"; U.S. patent publication No. US 2015/044517, filed 8/2014 as application No. 14/455,230 and published 2/12/2015 entitled "Self-Healing Electrode Protection in Electrochemical Cells"; U.S. patent publication No. US 2015/0236322, published on 20/8/2015, filed on 19/2/2014 as application No. 14/184,037 and entitled "Electrode Protection Using Electrode-Inhibiting Ion Conductor"; and U.S. patent publication No. US 2016/0072132, filed as application No. 14/848,659 on 9/2015 9 and published on 10/3/2016, entitled "Protective Layers in Lithium-Ion Electrochemical Cells and Associated Electrodes and Methods".

U.S. provisional application No. 62/785,332, entitled "isolated Electrodes and Associated Electrodes and Methods," filed on 12/27 of 2018, which is incorporated herein by reference in its entirety for all purposes. U.S. provisional application No. 62/785,335, entitled "Electrodes, Heaters, Sensors, and Associated optics and Methods", filed on 27.12.2018, is incorporated herein by reference in its entirety for all purposes. U.S. provisional application No. 62/785,338, entitled "Folded Electrochemical Devices and Associated Methods and Systems," filed on 2018, 12, 27, is incorporated herein by reference in its entirety for all purposes.

While several embodiments of the invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present disclosure is directed to each individual feature, system, article, material, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, and/or methods, if such features, systems, articles, materials, and/or methods are not mutually inconsistent, is included within the scope of the present invention.

The indefinite articles "a" and "an" as used herein in the specification and in the claims are to be understood as meaning "at least one" unless clearly indicated to the contrary.

The phrase "and/or" as used herein in the specification and in the claims should be understood to mean "either or both" of the elements so combined, i.e., elements that are present in combination in some cases and separately in other cases. Other elements may optionally be present, whether related or unrelated to those elements specifically identified, other than those explicitly identified by the "and/or" clause, unless explicitly stated to the contrary. Thus, as a non-limiting example, when used in conjunction with open language such as "including," references to "a and/or B" may refer in one embodiment to a without B (optionally including elements other than B); in another embodiment, B is a free of a (optionally including elements other than a); in yet another embodiment, both a and B (optionally including other elements); and the like.

As used herein in the specification and claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when items in a list are separated, "or" and/or "should be interpreted as being inclusive, i.e., including at least one of a plurality of elements or a list of elements, but also including more than one, and optionally including other unlisted items. Only terms explicitly indicated to the contrary, such as "only one" or "exactly one," or "consisting of," when used in a claim, shall mean including a plurality of elements or exactly one of a list of elements. In general, when preceded by an exclusive term (e.g., "any," "one," "only one," or "exactly one"), the term "or" as used herein should be interpreted merely as indicating an exclusive alternative (i.e., "one or the other, not both"). "consisting essentially of" when used in the claims shall have the ordinary meaning as used in the art of patent law.

As used herein in the specification and in the claims, the phrase "at least one of" in reference to a list of one or more elements should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including each and at least one of each element specifically listed within the list of elements, and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified in the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of a and B" (or, equivalently, "at least one of a or B," or, equivalently, "at least one of a and/or B") may refer, in one embodiment, to at least one a (optionally including more than one a) without B (and optionally including elements other than B); in another embodiment, may refer to at least one B (optionally including more than one B), with no a present (and optionally including elements other than a); in yet another embodiment, may refer to at least one a (optionally including more than one a) and at least one B (optionally including more than one B) (and optionally including other elements); and the like.

In the claims as well as in the description above, all transitional phrases such as "comprising", "including", "carrying", "having", "containing", "involving", "holding", and the like are to be understood as open-ended, i.e. to mean including but not limited to. As described in united states patent office patent examination program manual section 2111.03, only the transitional phrase "consisting of and" consisting essentially of shall be the closed or semi-closed transitional phrase, respectively.

Claims

1. An article of manufacture, comprising:

a substrate;

a plurality of discrete electrode segments adjacent to the substrate, the electrode segments comprising an electrode active material; and

a collector domain comprising:

a collector bus electronically coupled to the discrete electrode segments; and

a plurality of collector segments, each collector segment electronically coupled to an electrode segment,

wherein, for each of the collector segments, the collector segment is electronically coupled to the collector bus via at least one collector bridge.

2. The article of claim 1, wherein, for each discrete electrode segment, the discrete electrode segment is electronically coupled to the collector bus via at least one collector segment.

3. The article of any one of claims 1-2, wherein, for each current collector segment, the current collector segment is at least partially disposed between the substrate and the electrode segment to which the current collector segment is electronically coupled.

4. The article of any of claims 1-3, wherein the article is configured such that: when the temperature of the article reaches a threshold temperature, at least one of the collector bridges no longer couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced volume change of the substrate.

5. The article of any one of claims 1 to 4, wherein the article is configured such that: when the temperature of the article reaches a threshold temperature, at least one of the discrete electrode segments is no longer electronically coupled to the current collector bus due, at least in part, to the thermally-induced volumetric change of the substrate.

6. The article of any one of claims 1 to 5, wherein the heat-induced change in volume of the substrate is an increase in volume of the substrate.

7. The article of any one of claims 1 to 6, wherein the article is configured such that: upon the temperature of the article reaching a threshold temperature, at least one of the collector bridges is subject to an ultimate tensile failure such that the at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced change in volume of the substrate.

8. The method of any of claims 1 to 7, wherein the substrate has a coefficient of thermal expansion greater than a coefficient of thermal expansion of the at least one current collector bridge.

9. The article of any one of claims 4 to 5, wherein the heat-induced change in volume of the substrate is a decrease in volume of the substrate.

10. The article of any one of claims 4 to 5 and 9, wherein the substrate has a negative coefficient of thermal expansion at the threshold temperature.

11. The article of any one of claims 1 to 10, wherein the substrate comprises a heat shrink film.

12. The article of any one of claims 1 to 11, wherein the substrate comprises polyvinyl alcohol.

13. The article of any one of claims 1 to 12, wherein the article is configured such that: when the article reaches a threshold current, at least one of the collector bridges mechanically deforms such that a collector segment coupled to that collector bridge is no longer electronically coupled to the collector bus.

14. The article of any one of claims 4 to 13, wherein the threshold temperature has a value greater than or equal to 50 ℃.

15. The article of any one of claims 4 to 14, wherein the threshold temperature has a value less than or equal to 150 ℃.

16. The article of any one of claims 13-15, wherein the threshold current has a value greater than or equal to 10A.

17. The article of any one of claims 13-16, wherein the threshold current has a value less than or equal to 120A.

18. The article of any one of claims 1 to 17, further comprising a heater adjacent to the substrate, the heater configured to heat at least a portion of the substrate.

19. The article of any of claims 1-18, wherein a thickness of the current collector bus is at least 3 times greater than a thickness of at least one of the current collector bridges.

20. The article of any of claims 1-19, wherein the current collector bus and the plurality of current collector segments are part of a unitary structure.

21. The article of any one of claims 1 to 20, wherein the electrode segment comprises lithium metal and/or a lithium alloy as the electrode active material.

22. The article of any of claims 1-21, wherein the at least one current collector bridge and the substrate have a thermal expansion difference of greater than or equal to 10 ℃ and less than or equal to 100 ℃, wherein the thermal expansion difference is expressed as:

Wherein A is₁Is the area of the at least one current collector bridge, A₂Is thatArea of the substrate, a₁Is the linear expansion coefficient of the at least one current collector bridge, a₂Is the linear expansion coefficient of the substrate, E₁Is the modulus of elasticity, E, of the at least one current collector bridge₂Is the modulus of elasticity of the substrate, and σ_ult，1Is the ultimate tensile strength of the at least one current collector bridge.

23. The article of any one of claims 18 to 22, wherein the heater is proximate to the substrate.

24. The article of any one of claims 18 to 23, wherein the heater comprises a film.

25. The article of any one of claims 18 to 24, wherein the heater comprises a wire.

26. The article of any one of claims 18 to 25, wherein the heater comprises a metal or metal alloy.

27. The article of any one of claims 18 to 26, wherein the heater comprises a nickel alloy, stainless steel, graphite, a silicon-based compound, or a combination thereof.

28. The article of any one of claims 18 to 27, wherein the heater is configured to have a resistance greater than or equal to 50 Ω and less than or equal to 1000 Ω.

29. The article of any one of claims 18 to 28, wherein the heater is not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

30. The article of any one of claims 18 to 29, wherein at least a portion of the heater is coated with an electrically insulating material.

31. The article of any one of claims 1 to 30, wherein the article further comprises one or more sensors adjacent to the substrate, the one or more sensors configured to respond to a condition of the article.

32. The article of claim 31, wherein the one or more sensors are proximate to the substrate.

33. The article of any one of claims 31 to 32, wherein at least one of the sensors is a temperature sensor configured to respond to a temperature of the article.

34. The article of any one of claims 31 to 33, wherein at least one of the sensors is a pressure sensor configured to respond to pressure experienced by the article.

35. The article of any one of claims 33 to 34, wherein the temperature sensor comprises a thermocouple and/or a thermistor.

36. The article of any one of claims 33 to 35, wherein the temperature sensor is or comprises a film.

37. The article of any one of claims 33 to 36, wherein the temperature sensor comprises a resistance temperature detector.

38. The article of any one of claims 33 to 36, wherein the temperature sensor comprises platinum, nickel, copper, iron, or a combination thereof.

39. The article of any one of claims 33 to 37, wherein the temperature sensor comprises a non-conductive layer, optionally comprising a ceramic.

40. The article of any one of claims 34 to 39, wherein the pressure sensor is a capacitance-based pressure sensor.

41. The article of any one of claims 34 to 40, wherein the pressure sensor comprises: two electrodes; and an electrically insulating material positioned between the two electrodes.

42. The article of claim 41, wherein the electrically insulating material comprises a polymeric material.

43. The article of any one of claims 34 to 42, wherein the pressure sensor is a strain gauge.

44. The article of any one of claims 34 to 43, wherein the pressure sensor comprises a piezoelectric sensor or a piezoresistive sensor.

45. The article of any one of claims 34 to 44, wherein the pressure sensor is or comprises a film.

46. The article of any one of claims 34 to 45, wherein the one or more sensors are configured to be electronically coupled to an external circuit.

47. The article of any one of claims 34 to 46, wherein the one or more sensors are not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

48. The article of any one of claims 34 to 47, wherein at least a portion of the one or more sensors are coated with an electrically insulating material.

49. The article of any one of claims 1 to 48, wherein the article is foldable.

50. The article of claim 49, wherein the heater and/or the one or more sensors are positioned between folded portions of the article when the article is folded.

51. An article of manufacture, comprising:

a substrate;

a collector domain comprising a collector bus electronically coupled to the discrete electrode segments;

Wherein the article is configured such that: when the temperature of the article reaches a threshold temperature, at least one of the electrode segments is no longer electronically coupled to the current collector bus due, at least in part, to the thermally-induced volumetric change of the substrate.

52. The article of claim 51, wherein the heat-induced change in volume of the substrate is an increase in volume of the substrate.

53. The article of claim 51, wherein the thermally-induced change in volume of the substrate is a decrease in volume of the substrate.

54. The article of any one of claims 51-53, wherein the substrate has a negative coefficient of thermal expansion at the threshold temperature.

55. The article of any one of claims 51-54, wherein the substrate comprises a heat shrink film.

56. The article of any one of claims 51 to 55, wherein the substrate comprises polyvinyl alcohol.

57. The article of any one of claims 51 to 56, further comprising a heater adjacent to the substrate, the heater configured to heat at least a portion of the article.

58. The article of any one of claims 51 to 57, wherein the electrode segment comprises lithium metal and/or a lithium alloy as the electrode active material.

59. The article of any one of claims 51 to 58, wherein the collector domain further comprises a plurality of collector segments, each collector segment electronically coupled to an electrode segment, wherein for each of the collector segments, the collector segment is electronically coupled to the collector bus via at least one collector bridge.

60. The article according to claim 59, wherein for each discrete electrode segment, the discrete electrode segment is electronically coupled to the collector bus via at least one collector segment.

61. The article of any one of claims 59 to 60, wherein for each current collector segment, the current collector segment is at least partially disposed between the substrate and the electrode segment to which the current collector segment is electronically coupled.

62. The article of any one of claims 59 to 61, wherein the article is configured such that: when the temperature of the article reaches the threshold temperature, at least one of the collector bridges no longer couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced volume change of the substrate.

63. The article of any one of claims 59 to 62, wherein upon the temperature of the article reaching the threshold temperature, at least one of the collector bridges is subject to an ultimate tensile failure such that at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to thermally-induced volumetric changes of the substrate.

64. The method of any one of claims 59 to 63, wherein the substrate has a coefficient of thermal expansion that is greater than a coefficient of thermal expansion of the at least one current collector bridge.

65. The article of any one of claims 59 to 64, wherein the article is configured such that: when the temperature of the article reaches a threshold current, at least one of the collector bridges mechanically deforms such that a collector segment coupled thereto is no longer electrically coupled to the collector bus.

66. The article of any one of claims 51-65, wherein the threshold temperature has a value greater than or equal to 50 ℃.

67. The article of any one of claims 51-65, wherein the threshold temperature has a value less than or equal to 150 ℃.

68. The article of any one of claims 65-67, wherein the threshold current has a value greater than or equal to 10A.

69. The article of any one of claims 65-68, wherein the threshold current has a value less than or equal to 120A.

70. The article of any of claims 59 to 69, wherein the thickness of the current collector bus is at least 3 times greater than the thickness of at least one of the current collector bridges.

71. The article of any one of claims 59 to 70, wherein the current collector bus and the plurality of current collector segments are part of a unitary structure.

72. The article of any of claims 59 to 71, wherein the at least one current collector bridge and the substrate have a thermal expansion difference of greater than or equal to 10 ℃ and less than or equal to 100 ℃, wherein the thermal expansion difference is expressed as:

wherein A is₁Is the area of the at least one current collector bridge, A₂Is the area of the substrate, a₁Is the linear expansion coefficient of the at least one current collector bridge, a₂Is the linear expansion coefficient of the substrate, E₁Is the modulus of elasticity, E, of the at least one current collector bridge₂Is the modulus of elasticity of the substrate, and σ_ult，1Is the ultimate tensile strength of the at least one current collector bridge.

73. The article of any one of claims 57-72, wherein the heater is immediately adjacent to the substrate.

74. The article of any one of claims 57-73, wherein the heater comprises a film.

75. The article of any one of claims 57-74, wherein the heater comprises a wire.

76. The article of any one of claims 57-75, wherein the heater comprises a metal or metal alloy.

77. The article of any one of claims 57-76, wherein the heater comprises nichrome, graphite, a silicon-based compound, or a combination thereof.

78. The article of any one of claims 57-77, wherein the heater is configured to have a resistance greater than or equal to 50 Ω and less than or equal to 1,000 Ω.

79. The article of any one of claims 57-78, wherein the heater is not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

80. The article of any one of claims 57-79, wherein at least a portion of the heater is coated with an electrically insulating material.

81. The article of any one of claims 51 to 80, wherein the article further comprises one or more sensors adjacent to the substrate, the one or more sensors configured to respond to a condition of the article.

82. The article of claim 81, wherein the one or more sensors are in close proximity to the substrate.

83. The article of any one of claims 81-82, wherein at least one of the sensors is a temperature sensor configured to respond to a temperature of the article.

84. The article of any one of claims 81-83, wherein at least one of the sensors is a pressure sensor configured to respond to pressure experienced by the article.

85. The article of any one of claims 83-84, wherein the temperature sensor comprises a thermocouple and/or a thermistor.

86. The article of any one of claims 83 to 85, wherein the temperature sensor is or comprises a film.

87. The article of any one of claims 83-86, wherein the temperature sensor comprises a resistance temperature detector.

88. The article of any one of claims 83-87, wherein the temperature sensor comprises platinum, nickel, copper, iron, or a combination thereof.

89. The article of any one of claims 83 to 87, wherein the temperature sensor comprises a non-conductive layer, optionally comprising a ceramic.

90. The article of any one of claims 84 to 85, wherein the pressure sensor is a capacitance-based pressure sensor.

91. The article of any one of claims 84 to 90, wherein the pressure sensor comprises: two electrodes; and an electrically insulating material positioned between the two electrodes.

92. The article of claim 91, wherein the electrically insulating material comprises a polymeric material.

93. The article of any one of claims 84-92, wherein the pressure sensor is a strain gauge.

94. The article of any one of claims 84 to 93, wherein the pressure sensor comprises a piezoelectric sensor or a piezoresistive sensor.

95. The article of any one of claims 84 to 94, wherein the pressure sensor is or comprises a film.

96. The article of any one of claims 81-95, wherein the one or more sensors are configured to be electronically coupled to an external circuit.

97. The article of any one of claims 81 to 96, wherein the one or more sensors are not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

98. The article of any one of claims 81 to 97, wherein at least a portion of the one or more sensors are coated with an electrically insulating material.

99. The article of any one of claims 51-98, wherein the article is foldable.

100. The article of claim 99, wherein the heater and/or the one or more sensors are positioned between folded portions of the article when the article is folded.

101. A method, comprising:

changing a volume of a substrate that is part of an electrochemical device during charging and/or discharging of the electrochemical device, the electrochemical device comprising:

a substrate, a first electrode and a second electrode,

a plurality of discrete electrode segments adjacent to the substrate, the electrode segments comprising an electrode active material, an

wherein changing the volume of the substrate causes, at least in part, a loss of electronic coupling between at least one of the electrode segments and the current collector bus.

102. The method of claim 101, wherein changing the volume of the substrate comprises heating the substrate.

103. The method of any one of claims 101 to 102, wherein altering the volume of the substrate comprises increasing the volume of the substrate.

104. The method of any one of claims 101 to 102, wherein altering the volume of the substrate comprises reducing the volume of the substrate.

105. The method of any one of claims 102 to 104, wherein heating the substrate comprises charging and/or discharging the electrochemical device such that heat is generated by the charging and/or discharging.

106. The method of any one of claims 102 to 105, wherein heating the substrate comprises heating the substrate via a heater that is part of the electrochemical device.

107. The method of any one of claims 101 to 106, wherein a loss of electronic coupling of the electrode segment to the current collector bus occurs when the temperature of the electrochemical device reaches a threshold temperature.

108. The method of claim 107, wherein the substrate has a negative coefficient of thermal expansion at the threshold temperature.

109. The method of any one of claims 101 to 108, wherein the substrate comprises a heat shrink film.

110. The method of any one of claims 101 to 109, wherein the substrate comprises polyvinyl alcohol.

111. The method of any one of claims 101 to 110, wherein the electrode segment comprises lithium metal and/or a lithium alloy as the electrode active material.

112. The method of any of claims 101-111, wherein the collector domain further comprises a plurality of collector segments, each collector segment electronically coupled to an electrode segment, wherein, for each of the collector segments, the collector segment is electronically coupled to the collector bus via at least one collector bridge.

113. The method of claim 112, wherein for each discrete electrode segment, the discrete electrode segment is electronically coupled to the collector bus via at least one collector segment.

114. The method of any of claims 112 to 113, wherein for each current collector segment, the current collector segment is at least partially disposed between the substrate and the electrode segment to which the current collector segment is electronically coupled.

115. The method of any of claims 112 to 114, wherein changing the volume of the substrate causes, at least in part, at least one of the collector bridges to no longer couple the collector segment associated with that collector bridge to the collector bus.

116. The method of claims 112-115, wherein heating the substrate to the threshold temperature or a temperature above the threshold temperature subjects the at least one of the collector bridges to an extreme tensile failure such that the at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus.

117. The method of any of claims 112 to 116, wherein the substrate has a coefficient of thermal expansion greater than a coefficient of thermal expansion of the at least one current collector bridge.

118. The method of any one of claims 112 to 117, wherein charging and/or discharging of the electrochemical device causes current to mechanically deform at least one of the collector bridges such that at least one collector segment is decoupled from the collector bus.

119. The method of any one of claims 107-118, wherein the threshold temperature has a value greater than or equal to 50 ℃.

120. The method of any one of claims 107-119, wherein the threshold temperature has a value less than or equal to 150 ℃.

121. The method of any one of claims 115 to 120, wherein the current has a value greater than or equal to 10A.

122. The method of any one of claims 115 to 121, wherein the current has a value less than or equal to 120A.

123. The method of any of claims 111-121, wherein a thickness of the current collector bus is at least 3 times greater than a thickness of at least one of the current collector bridges.

124. The method of any of claims 111-123, wherein the collector bus and the plurality of collector segments are part of a unitary structure.

125. The method of any one of claims 101 to 124, wherein the electrochemical device is capable of being charged and/or discharged after the loss of electronic coupling between the at least one of the electrode segments and the collector bus.

126. The method of any of claims 112-125, wherein the at least one current collector bridge and the substrate have a thermal expansion difference greater than or equal to 10 ℃ and less than or equal to 100 ℃, wherein the thermal expansion difference is expressed as:

127. The method of any one of claims 106 to 126, wherein the heater is adjacent to the substrate.

128. The method of any one of claims 106 to 127, wherein the heater is in close proximity to the substrate.

129. The method of any one of claims 106 to 128, wherein the heater is a thin film.

130. The method of any one of claims 106 to 129, wherein the heater comprises a wire.

131. The method of any one of claims 106 to 130, wherein the heater comprises a metal or metal alloy.

132. The method of any one of claims 106 to 131 wherein the heater comprises nichrome, graphite, a silicon-based compound, or a combination thereof.

133. The method of any one of claims 106 to 132, wherein the heater is configured to have a resistance greater than or equal to 50 Ω and less than or equal to 1,000 Ω.

134. The method of any one of claims 106 to 133, wherein the heater is not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

135. The method of any one of claims 106 to 134, wherein at least a portion of the heater is coated with an electrically insulating material.

136. The method of any one of claims 101 to 135, wherein the change in volume of the substrate is initiated in response to a signal from one or more sensors that are part of the electrochemical device, wherein the one or more sensors are configured to respond to a condition of the electrochemical device.

137. The method of claim 136, wherein the one or more sensors are adjacent to the substrate.

138. The method of any one of claims 136 to 137, wherein the one or more sensors are in close proximity to the substrate.

139. The method of any one of claims 136 to 138, wherein at least one of the sensors is a temperature sensor configured to respond to a temperature of the electrochemical device.

140. The method of any one of claims 136 to 139, wherein at least one of the sensors is a pressure sensor configured to respond to a pressure experienced by the electrochemical device.

141. The method of any one of claims 139 to 140, wherein the temperature sensor comprises a thermocouple and/or a thermistor.

142. The method of any one of claims 139 to 141, wherein the temperature sensor is or comprises a membrane.

143. The method of any one of claims 139 to 142, wherein the temperature sensor comprises a resistance temperature detector.

144. The method of any one of claims 139 to 143, wherein the temperature sensor comprises platinum, nickel, copper, iron, or a combination thereof.

145. The method of any one of claims 139 to 144, wherein the temperature sensor comprises a non-conductive layer, optionally comprising a ceramic.

146. The method of any one of claims 140-145, wherein the pressure sensor is a capacitance-based pressure sensor.

147. The method of any one of claims 140-146, wherein the pressure sensor comprises: two electrodes; and an electrically insulating material positioned between the two electrodes.

148. The method of claim 147, wherein the electrically insulating material comprises a polymer material.

149. The method of any one of claims 140-148, wherein the pressure sensor is a strain gauge.

150. The method of any one of claims 140 to 149, wherein the pressure sensor comprises a piezoelectric sensor or a piezoresistive sensor.

151. The method of any one of claims 140 to 150, wherein the pressure sensor is or comprises a membrane.

152. The method of any one of claims 136 to 151, wherein the one or more sensors are configured to be electronically coupled to an external circuit.

153. The method of any one of claims 136 to 152, wherein the one or more sensors are not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

154. The method of any one of claims 136 to 153, wherein at least a portion of the one or more sensors are coated with an electrically insulating material.

155. The method of any one of claims 101 to 154, wherein the electrochemical device is foldable.

156. The method of any one of claims 136 to 155, wherein the heater and/or the one or more sensors are positioned between folded portions of the electrochemical device at the time of the electrochemical folding.

157. An electrochemical device, comprising:

the article of any one of claims 1 to 100;

a second electrode comprising an electrode active material, the second electrode having a polarity opposite to a polarity of the plurality of discrete electrode segments; and

a separator between the article and the second electrode.

158. The electrochemical device of claim 157, wherein the electrochemical device is collapsible.

159. An article of manufacture, comprising:

a substrate;

a plurality of discrete electrode segments adjacent to the substrate, the electrode segments comprising an electrode active material;

a collector domain comprising a collector bus electronically coupled to the discrete electrode segments; and

a heater adjacent to the substrate, wherein the heater is configured to heat at least a portion of the article.

160. The article of claim 159, wherein the heater is proximate to the substrate.

161. The article of any one of claims 159 to 160, wherein the heater comprises a film.

162. The article of any one of claims 159 to 161, wherein the heater comprises a wire.

163. The article of any of claims 159-162 wherein the heater comprises a metal or metal alloy.

164. The article of any one of claims 159 to 163, wherein the heater comprises nichrome, graphite, a silicon-based compound, or a combination thereof.

165. The article of any one of claims 159 to 164, wherein the heater is configured to have a resistance greater than or equal to 50 Ω and less than or equal to 1000 Ω.

166. The article of any one of claims 159 to 165, wherein the heater is not electrically coupled to the plurality of discrete electrode segments or the current collector domain.

167. The article of any one of claims 159 to 166, wherein at least a portion of the heater is coated with an electrically insulating material.

168. The article of any one of claims 159 to 167, wherein the article is foldable.

169. The article of claim 168, wherein the heater is positioned between folded portions of the article when the article is folded.

170. The article of any one of claims 159 to 169, wherein the article is configured such that: when the temperature of the article reaches a threshold temperature, at least one of the electrode segments is no longer electronically coupled to the current collector bus due, at least in part, to the thermally-induced volumetric change of the substrate.

171. The article of any one of claims 159 to 170, wherein the heater is configured to cause at least a portion of a thermally-induced volumetric change of the substrate.

172. The article of any one of claims 170 to 171, wherein the heat-induced change in volume of the substrate is an increase in volume of the substrate.

173. The article of any one of claims 170 to 171, wherein the heat-induced change in volume of the substrate is a decrease in volume of the substrate.

174. The article of any one of claims 159 to 173, wherein the substrate has a negative coefficient of thermal expansion at the threshold temperature.

175. The article of any one of claims 159 to 174, wherein the substrate comprises a heat shrink film.

176. The article of any one of claims 159 to 175, wherein the substrate comprises polyvinyl alcohol.

177. The article of any one of claims 159 to 176, wherein the electrode segment comprises lithium metal and/or a lithium alloy as the electrode active material.

178. The article of any one of claims 159 to 177, wherein the collector domain further comprises a plurality of collector segments, each collector segment electronically coupled to an electrode segment, wherein for each of the collector segments, the collector segment is electronically coupled to the collector bus via at least one collector bridge.

179. The article of claim 178, wherein for each discrete electrode segment, the discrete electrode segment is electronically coupled to the collector bus via at least one collector segment.

180. The article of any of claims 178-179, wherein, for each current collector segment, the current collector segment is at least partially disposed between the substrate and the electrode segment to which the current collector segment is electronically coupled.

181. The article of any one of claims 178-180, wherein the article is configured such that: when the temperature of the article reaches the threshold temperature, at least one of the collector bridges no longer couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced volume change of the substrate.

182. The article of any of claims 178-181, wherein upon the temperature of the article reaching the threshold temperature, at least one of the collector bridges experiences an ultimate tensile failure such that the at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to thermally-induced volumetric changes of the substrate.

183. The article of any of claims 178-182, wherein the substrate has a coefficient of thermal expansion that is greater than a coefficient of thermal expansion of the at least one current collector bridge.

184. The article of any one of claims 178-183, wherein the article is configured such that: when the temperature of the article reaches a threshold current, at least one of the collector bridges mechanically deforms such that a collector segment coupled thereto is no longer electrically coupled to the collector bus.

185. The article of any one of claims 170-184, wherein the threshold temperature has a value greater than or equal to 50 ℃.

186. The article of any one of claims 170-185, wherein the threshold temperature has a value less than or equal to 150 ℃.

187. The article of any one of claims 184-186, wherein the threshold current has a value greater than or equal to 10A.

188. The article of any of claims 184-187, wherein the threshold current has a value less than or equal to 120A.

189. The article of any of claims 178-188, wherein the thickness of the current collector bus is at least 3 times greater than the thickness of at least one of the current collector bridges.

190. The article of any of claims 178-189, wherein the current collector bus and the plurality of current collector segments are part of a unitary structure.

191. The article of any of claims 178-190, wherein the at least one current collector bridge and the substrate have a thermal expansion difference of greater than or equal to 10 ℃ and less than or equal to 100 ℃, wherein the thermal expansion difference is expressed as:

wherein A is₁Is the area of the at least one current collector bridge, A₂Is the area of the substrate, a₁Is the linear expansion coefficient of the at least one current collector bridge, a₂Is the linear expansion coefficient of the substrate, E₁Is the modulus of elasticity, E, of the at least one current collector bridge₂Is the modulus of elasticity of the substrate, and σ_ult，1Is the ultimate tensile strength of at least one current collector bridge.

192. The article of any one of claims 159-191, further comprising one or more sensors adjacent the substrate, the one or more sensors configured to respond to a condition of the article.

193. The article of claim 192, wherein the one or more sensors are directly adjacent to the substrate.

194. The article of any one of claims 192-193, wherein at least one of the sensors is a temperature sensor.

195. The article of any one of claims 192-194, wherein at least one of the sensors is a pressure sensor.

196. The article of any one of claims 192 to 195, wherein the heater is configured to be actuated by the one or more sensors.

197. An article of manufacture, comprising:

a substrate;

a plurality of discrete electrode segments adjacent to the substrate, the electrode segments comprising an electrode active material,

one or more sensors adjacent to the substrate, the one or more sensors configured to respond to a condition of the article.

198. The article of claim 197, wherein the one or more sensors are in close proximity to the substrate.

199. The article of any one of claims 197-198, wherein at least one of the sensors is a temperature sensor configured to respond to a temperature of the article.

200. The article of any one of claims 197-199, wherein at least one of the sensors is a pressure sensor configured to respond to pressure experienced by the article.

201. The article of any one of claims 199-200, wherein the temperature sensor comprises a thermocouple and/or a thermistor.

202. The article of any one of claims 199-201, wherein the temperature sensor is or comprises a film.

203. The article of any one of claims 199-202, wherein the temperature sensor comprises a resistance temperature detector.

204. The article of any one of claims 199-203, wherein the temperature sensor comprises platinum, nickel, copper, iron, or a combination thereof.

205. The article of any one of claims 199-204, wherein the temperature sensor comprises a non-conductive layer, optionally comprising a ceramic.

206. The article of any one of claims 200 to 205, wherein the pressure sensor is a capacitance-based pressure sensor.

207. The article of any one of claims 200 to 206, wherein the pressure sensor comprises: two electrodes; and an electrically insulating material located between the two electrodes.

208. The article of claim 207, wherein the electrically insulating material comprises a polymeric material.

209. The article of any one of claims 200-207, wherein the pressure sensor is a strain gauge.

210. The article of any one of claims 200 to 208, wherein the pressure sensor comprises a piezoelectric sensor or a piezoresistive sensor.

211. The article of any one of claims 200 to 210, wherein the pressure sensor is or comprises a film.

212. The article of any one of claims 197-211, wherein the one or more sensors are configured to be electronically coupled to an external circuit.

213. The article of any one of claims 197-212, wherein the one or more sensors are not electronically coupled to the plurality of discrete electrode segments or the current collector domain.

214. The article of any one of claims 197-213, wherein at least a portion of the one or more sensors are coated with an electrically insulating material.

215. The article of any one of claims 197-214, wherein the article is foldable.

216. The article of claim 215, wherein the one or more sensors are positioned between folded portions of the article when the article is folded.

217. The article of any one of claims 197-216, wherein the article is configured such that: when the temperature of the article reaches a threshold temperature, at least one of the electrode segments is no longer electronically coupled to the current collector bus due, at least in part, to the thermally-induced volumetric change of the substrate.

218. The article of claim 217, wherein the thermally-induced change in volume of the substrate is an increase in volume of the substrate.

219. The article of claim 217, wherein the thermally-induced change in volume of the substrate is a decrease in volume of the substrate.

220. The article of any one of claims 197-219, wherein the substrate has a negative coefficient of thermal expansion at the threshold temperature.

221. The article of any one of claims 197-220, wherein the substrate comprises a heat shrinkable film.

222. The article of any one of claims 197-221, wherein the substrate comprises polyvinyl alcohol.

223. The article of any one of claims 197 to 222, wherein the electrode segment comprises lithium metal and/or a lithium alloy as the electrode active material.

224. The article of any of claims 217-223, wherein the current collector domain further comprises a plurality of current collector segments, each current collector segment electronically coupled to an electrode segment, wherein for each of the current collector segments, the current collector segment is electronically coupled to the current collector bus via at least one current collector bridge.

225. The article of claim 224, wherein for each discrete electrode segment, the discrete electrode segment is electronically coupled to the collector bus via at least one collector segment.

226. The article of any of claims 224 to 225, wherein, for each current collector segment, the current collector segment is at least partially disposed between the substrate and the electrode segment to which the current collector segment is electronically coupled.

227. The article of any one of claims 224 to 226, wherein the article is configured such that: when the temperature of the article reaches the threshold temperature, at least one of the collector bridges no longer couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to the thermally-induced volume change of the substrate.

228. The article of any one of claims 224-227, wherein at least one of the collector bridges experiences an ultimate tensile failure when the temperature of the article reaches the threshold temperature such that the at least one of the collector bridges no longer electronically couples the collector segment associated with that collector bridge to the collector bus due, at least in part, to thermally-induced volumetric changes of the substrate.

229. The article of any one of claims 224 to 228, wherein the substrate has a coefficient of thermal expansion that is greater than a coefficient of thermal expansion of the at least one current collector bridge.

230. The article of any one of claims 224 to 229, wherein the article is configured such that: when the temperature of the article reaches a threshold current, at least one of the collector bridges mechanically deforms such that a collector segment coupled thereto is no longer electrically coupled to the collector bus.

231. The article of any of claims 217-230, wherein the threshold temperature has a value greater than or equal to 50 ℃.

232. The article of any of claims 217-231, wherein the threshold temperature has a value less than or equal to 150 ℃.

233. The article of any one of claims 230-232, wherein the threshold current has a value greater than or equal to 10A.

234. The article of any one of claims 230-233, wherein the threshold current has a value less than or equal to 120A.

235. The article of any of claims 224-234, wherein the thickness of the current collector bus is at least 3 times greater than the thickness of at least one of the current collector bridges.

236. The article of any of claims 224-235, wherein the current collector bus and the plurality of current collector segments are part of a unitary structure.

237. The article of any of claims 224 to 227, wherein the at least one current collector bridge and the substrate have a thermal expansion difference of greater than or equal to 10 ℃ and less than or equal to 100 ℃, wherein the thermal expansion difference is expressed as:

238. The article of any one of claims 197-237, further comprising a heater adjacent the substrate.

239. The article of claim 238, wherein the heater is proximate the substrate.

240. The article of any one of claims 238-239, wherein the heater is configured to be actuated by the one or more sensors.

241. A method, comprising:

heating at least a portion of an electrochemical device using a heater as part of the electrochemical device, the electrochemical device comprising:

a substrate, a first electrode and a second electrode,

A collector domain comprising a collector bus electronically coupled to the discrete electrode segments.

242. The method of claim 241 wherein the heater is adjacent to the substrate.

243. The method of any one of claims 241 to 242, wherein the heater is in close proximity to the substrate.

244. The method of any one of claims 241 to 243, wherein the heating step is initiated at least partially in response to a signal from one or more sensors.

245. The method of claim 244, wherein the one or more sensors are part of the electrochemical device.

246. The method of any one of claims 244-245, wherein the one or more sensors are adjacent to the substrate.

247. The method of any one of claims 244 to 246, wherein said heater and/or said one or more sensors comprise a thin film.

248. A method, comprising:

detecting a condition of an electrochemical device based at least in part on a signal from a sensor that is part of the electrochemical device, the electrochemical device comprising:

a substrate, a first electrode and a second electrode,

249. The method of claim 248, wherein at least one of the sensors is a temperature sensor and the condition is temperature.

250. The method of claim 248, wherein at least one of the sensors is a pressure sensor and the condition is pressure.

251. The method of any one of claims 248-250, wherein the one or more sensors are adjacent to the substrate.

252. The method of any one of claims 248-251, wherein the one or more sensors are in close proximity to the substrate.

253. The method of any one of claims 248-252, wherein the one or more sensors comprise a membrane.

254. The method of any one of claims 248-253, further comprising: actuating a heater that is part of the electrochemical device based at least in part on the signal in response to the detecting step, and the heater is configured to heat at least a portion of the electrochemical device.

255. The method of claim 254 wherein the heater is adjacent to the substrate.

256. The method of any one of claims 254 to 255, wherein the heater is in close proximity to the substrate.

257. The method of any one of claims 254 to 256, wherein the heater comprises a membrane.

258. An electrochemical device, comprising:

the article of any one of claims 159 to 240;

a second electrode comprising an electrode active material, the second electrode having a polarity opposite to a polarity of the plurality of discrete electrode segments;

a separator between the article and the second electrode; and

a second current collector electronically coupled to the second electrode.

259. The electrochemical device of claim 258, wherein the electrochemical device is collapsible.

260. An electrochemical device, comprising:

A first anode portion comprising a first anode active surface portion;

a second anode portion comprising a second anode active surface portion, the second anode active surface portion facing the first anode active surface portion;

a third anode portion comprising a third anode active surface portion facing away from both the first anode active surface portion and the second anode active surface portion.

A fourth anode portion comprising a fourth anode active surface portion facing both the first anode active surface portion and the third anode active surface portion, wherein the third anode portion is positioned at least partially between the first anode portion and the fourth anode portion;

a first cathode portion comprising a first cathode active surface portion facing the first anode active surface portion;

a second cathode portion comprising a second cathode active surface portion facing the second anode active surface portion;

a third cathode portion comprising a third cathode active surface portion facing the third anode active surface portion;

a fourth cathode portion comprising a fourth cathode active surface portion facing the fourth anode active surface portion; and

A spacer arranged such that:

the first portion of the separator is between the first anode portion and the first cathode portion,

a second portion of the separator is between the second anode portion and the second cathode portion,

a third portion of the separator is between the third anode portion and the third cathode portion, and

a fourth portion of the separator is between the fourth anode portion and the fourth cathode portion;

wherein the electrochemical device is constructed and arranged to: applying an anisotropic force having a component perpendicular to the first anode active surface portion for at least one time period during charging and/or discharging of the device.

261. An electrochemical device, comprising:

a plurality of anode sections, a plurality of cathode sections, and a serpentine separator, the electrochemical device comprising the following sections arranged in the order listed:

a first anode portion comprising a first anode active surface portion;

a first spacer portion;

a first cathode portion comprising a first cathode active surface portion;

a second cathode portion comprising a second cathode active surface portion;

a second spacer portion;

A second anode portion comprising a second anode active surface portion;

a third anode portion comprising a third anode active surface portion;

a third spacer portion;

a third cathode portion comprising a third cathode active surface portion;

a fourth cathode portion comprising a fourth cathode active surface portion;

a fourth spacer portion; and

a fourth anode portion comprising a fourth anode active surface portion;

wherein the electrochemical device is constructed and arranged to apply an anisotropic force having a component perpendicular to the first anode active surface portion for at least one period of time during charging and/or discharging of the device.

262. An electrochemical device, comprising:

a first anode portion comprising a first anode active surface portion;

a third anode portion comprising a third anode active surface portion facing away from both the first anode active surface portion and the second anode active surface portion;

a spacer arranged such that:

wherein the electrochemical device includes a cumulative cathode active surface perimeter defined by a sum of perimeters of all cathode active surfaces of the electrochemical device, and at least 60% of the cumulative cathode active surface perimeter overlaps the anode active surface.

263. An electrochemical device, comprising:

a first anode portion comprising a first anode active surface portion;

a first spacer portion;

a first cathode portion comprising a first cathode active surface portion;

a second cathode portion comprising a second cathode active surface portion;

a second spacer portion;

a second anode portion comprising a second anode active surface portion;

a third anode portion comprising a third anode active surface portion;

a third spacer portion;

a third cathode portion comprising a third cathode active surface portion;

a fourth cathode portion comprising a fourth cathode active surface portion;

a fourth spacer portion; and

a fourth anode portion comprising a fourth anode active surface portion;

264. The electrochemical device of any one of claims 260 to 263, wherein each of the first anode portion, the second anode portion, the third anode portion, and the fourth anode portion is discrete.

265. The electrochemical device of any one of claims 260 to 263, wherein the first anode portion, the second anode portion, the third anode portion, and the fourth anode portion are part of a continuous anode.

266. The electrochemical device of any one of claims 260 to 265, wherein each of the first, second, third and fourth cathode portions is discrete.

267. The electrochemical device of any one of claims 260 to 265, wherein the first, second, third and fourth cathode portions are part of a continuous cathode.

268. The electrochemical device of any one of claims 260 to 267, wherein the first cathode portion forms at least a portion of a first face of a double-sided cathode and the second cathode portion forms at least a portion of a second face of the double-sided cathode.

269. The electrochemical device of any one of claims 260 to 268, comprising an anode current collector electronically coupled to each of the first, second, third and fourth anode portions.

270. The electrochemical device of any one of claims 260 to 269, comprising a cathode current collector electronically coupled to each of the first, second, third, and fourth cathode portions.

271. The electrochemical device of any one of claims 260 to 269, comprising: a first cathode current collector electronically coupled to the first cathode portion; and a second cathode current collector electronically coupled to the third cathode portion.

272. The electrochemical device of any one of claims 260 to 271, comprising a substrate adjacent to each of the first, second, third and fourth anode portions.

273. The electrochemical device of any one of claims 260 to 272, comprising: a first cathode current collector portion between the first cathode portion and the second cathode portion; and a second cathode current collector portion between the third cathode portion and the fourth cathode portion.

274. The electrochemical device of claim 273, wherein the first and second cathode current collector portions are discrete.

275. The electrochemical device of claim 273, wherein the first and second cathode current collector portions are part of a continuous cathode current collector.

276. The electrochemical device of any one of claims 260 to 275, comprising a base portion between the second anode portion and the third anode portion.

277. The electrochemical device of any one of claims 260 to 276, wherein each of the first, second, third and fourth anode portions comprises lithium and/or a lithium alloy as an anode active material.

278. The electrochemical device of any one of claims 260 to 261 and 264 to 277, wherein the electrochemical device comprises a cumulative cathode active surface perimeter defined by a sum of perimeters of all cathode active surfaces of the electrochemical device, and at least 60% of said cumulative cathode active surface perimeter overlaps with an anode active surface.

279. The electrochemical device of any one of claims 262-278, wherein the electrochemical device is constructed and arranged to apply an anisotropic force having a component perpendicular to the first anode active surface for at least one period of time during charging and/or discharging of the device.